CN102277099A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheets and surface protecting film - Google Patents

Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheets and surface protecting film Download PDF

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CN102277099A
CN102277099A CN2011102049911A CN201110204991A CN102277099A CN 102277099 A CN102277099 A CN 102277099A CN 2011102049911 A CN2011102049911 A CN 2011102049911A CN 201110204991 A CN201110204991 A CN 201110204991A CN 102277099 A CN102277099 A CN 102277099A
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solution
weight
methyl
ionic liquid
film
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天野立巳
安藤雅彦
奥村和人
小林夏希
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from JP2005010022A external-priority patent/JP4799873B2/en
Priority claimed from JP2005026357A external-priority patent/JP5008830B2/en
Priority claimed from JP2005026766A external-priority patent/JP3912686B2/en
Priority claimed from JP2005026737A external-priority patent/JP5019552B2/en
Priority claimed from JP2005026704A external-priority patent/JP4562180B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a pressure-sensitive composition comprising an ionic liquid and a polymer having a glass transition temperature Tg of 0 DEG C or lower as a base polymer as a pressure-sensitive adhesive composition in which electrification of a pressure-sensitive adhesive sheet can be prevented upon peeling, and staining property on an adherend can be reduced, and an antistatic pressure-sensitive sheet and surface protecting film using the pressure-sensitive adhesive composition.

Description

Binder composition, adhesive sheets and surface protective film
The application is 200510054498.0 divides an application, and the applying date of original application is on March 8th, 2005, and the denomination of invention of original application is binder composition, adhesive sheets and surface protective film
Technical field
The present invention relates to have the binder composition of static electricity resistance and use this binder composition and form the adhesive sheets and the surface protective film of the static electricity resistance of forms such as sheet or band shape.
The adhesive sheets that is made of antistatic adhering agent composition of the present invention is preferred for being easy to generate electrostatic plastics etc.Wherein, particularly as the adhesive sheet of the static electricity resistance that should avoid at electronic machine etc. using in the electrostatic purposes; and the surface protective film that uses in order to protect optical component surfaces such as polaroid, wavelength plate, optical compensating film, reflector plate, be very useful.
In addition, the present invention relates to the adhesion type optics that optics is provided with the binder layer of static electricity resistance.The present invention has been preferred for using the adhesion type optics of easy generation electrostatic plastic material.Wherein,, be very useful particularly as the adhesion type optics that is used for liquid-crystal display or touch panel etc.
Background technology
With regard to self adhesive tape, apply small pressure under the normal temperature at short notice and just can finish bondingly, in the joint of various article, can be used for various purposes.In addition, because self adhesive tape has cohesive force and elasticity,, therefore also can be used as surface protective film so in can be moderately bonding, also can strip down on the other hand from the shiny surface of hard.
Surface protective film generally is fitted on the protected body by the binder layer that is coated in the protective film side, and the purpose of use is damage or the pollution that produces in the processing, course of conveying that prevents at protected body.For example, for the polaroid that prevents to use on the panel of liquid-crystal display or wavelength plate opticses such as (wavelength plates) sustain damage or pollute, can be by the binder layer protective film of fitting.
In addition, on liquid-crystal display or touch panel, be laminated with various optical thin films such as the polaroid of the direction of vibration that is used to control, regulate light or phase differential or wavelength plate by bonding coat.
On these optical thin films; be pasted with barrier sheet in order to prevent damage or pollution and protection adhesive face; for prevent to process and course of conveying in the damage that produces or pollution etc. and be pasted with surface protective film etc., and with the form of this stickup operation that circulates.In addition, in the operation of applying optical thin film, do not need barrier sheet or surface protective film, so peel off, remove from optical thin film for protecting these optical thin films to use.
Above-mentioned optical thin film, tackiness agent, barrier sheet, surface protective film are to be made of plastic material, so the electrical insulating property height produces static when rubbing or peeling off.Therefore, when peeling off barrier sheet, surface protective film also produces static.In addition, static is a bigger problem in the manufacturing process of liquid-crystal display or touch panel.Because this static, on surface protective film or optics, can adhere to dust, thereby the problem of optics can occur polluting, the abnormal indication that causes by the liquid crystal aligning confusion, the bad situations such as electrostatic breakdown of peripheral circuit element.Therefore, take place, often surface protective film is implemented various anti-electrostatics at present and handle in order to prevent this unfavorable condition.
Up to now, as suppressing the charged trial of above-mentioned electrostatic, for example, disclose and in tackiness agent, add low-molecular-weight surfactant and from tackiness agent, tensio-active agent is transferred on the adherend and prevents the method (for example, referring to Patent Document 1) of static electrification.But these low-molecular-weight surfactants are exuded on the adhesive surface easily, when being applied to protective film, might pollute adherend.Therefore, when the adhesive application that will be added with low-molecular-weight surfactant during, there is the problem of the optical characteristics of damaging optics in the used for optical part protective film.
In addition, disclose in acryloid cement and to add the antistatic agent that constitutes by polyether polyol and an alkali metal salt and suppress the method (for example, referring to Patent Document 2) that antistatic agent oozes out to adhesive surface.But, knownly in this method, can not avoid oozing out of antistatic agent, when being applied to surface protective film, through after a while or under hot environment the contaminated problem of adherend taking place.
In addition, the single face that discloses plastics film is provided with the surface protective film (for example, referring to Patent Document 3) of antistatic backing.But problem is, in this surface protective film, owing to implemented the anti-electrostatic processing to supporting the side; although therefore can prevent surface protective film side static electrification; but can not prevent protected body static electrification, when stripper surface protective film from protected body, protected cognition is charged.
For example, disclose by sputtering at the method (for example, referring to Patent Document 4) that the conductive layer that forms Indium sesquioxide-stannic oxide on the polaroid carries out the anti-electrostatic processing.In addition, disclose the method (for example, referring to Patent Document 5) that on polaroid, forms the antistatic backing that constitutes by the ultraviolet curing based acrylic resin that has cooperated metal oxide particle.
But, in these methods, need to increase operation new, that be used on optics, forming antistatic backing, and the increase of this operation can reduce productivity, raises the cost.Therefore, be provided with the polaroid of antistatic backing, compare, have the problem that cost raises with the polaroid of not implementing the anti-electrostatic processing in the past.
On the other hand, known to adding polarized light member that antistatic agent formed the light diffusion layer with electrostatic-proof function to light diffusion layer (for example, refer to Patent Document 6), but this light diffusion layer is the layer that is used to make from the light diffusion of backlight, rather than be widely used in the layer of optics.
Patent documentation 1: the spy opens flat 9-165460 communique
Patent documentation 2: the spy opens flat 6-128539 communique
Patent documentation 3: the spy opens flat 11-256116 communique
Patent documentation 4: the spy opens flat 6-51121 communique
Patent documentation 5: the spy opens flat 2001-318230 communique
Patent documentation 6: the spy opens flat 2002-22960 communique
Summary of the invention
In view of above-mentioned situation, the object of the invention is to be provided at and can prevents the adhesive sheet static electrification when peeling off and can reduce the binder composition of the contaminative of adherend and adhesive sheets and the surface protective film that uses the static electricity resistance of said composition.
In addition, the objective of the invention is to, be provided at and prevent the adherend static electrification when peeling off and can reduce the binder composition of the contaminative of adherend and adhesive sheets and the surface protective film that uses the static electricity resistance of said composition.
And then; the objective of the invention is to; a kind of adhesion type optics is provided; wherein by giving electrostatic-proof function to the high binder layer of versatility; optics static electrification when peeling off barrier sheet or surface protective film can be prevented simple and easy and inexpensively, and the bounding force of binder layer can be fully kept.
The inventor etc. concentrate on studies for solving above-mentioned problem, found that and utilize binder composition as follows to achieve the above object, thereby finished the present invention.
That is, binder composition of the present invention is characterised in that, contains ionic liquid and is polymkeric substance below 0 ℃ as the second-order transition temperature Tg of base polymer.
Wherein, ionic liquid of the present invention is meant the melting salt (ionic compound) that (25 ℃) are in a liquid state under the room temperature.
According to the present invention, above-mentioned ionic liquid can be brought into play the effect of antistatic agent, and, can suppress oozing out of antistatic agent, even can obtain binder composition also lower after after a while or in the hot environment to the contaminative of adherend by using this liquid.Still indeterminate by the detailed reason of using ionic liquid to suppress to ooze out, but can be presumed as follows.
When the tensio-active agent that utilization has a chain alkyl etc. reached anti-static effect, tensio-active agent was exuded to the surface and together forms electric charge with airborne moisture and leaks layer.On the other hand, ionic liquid is liquid, so molecular motion specific surface promoting agent is easy, the generation of electric charge causes molecular transposition easily.Therefore, what work under the situation of ionic liquid is the charge neutralization mechanism that is caused by molecular transposition, so compare with tensio-active agent, still can not obtain the good anti-static effect even be not seeped into the surface.In addition, ionic liquid preferably at room temperature is liquid, so compare with solid salt, the interpolation in tackiness agent and dispersing or dissolving is easily carried out.And then ionic liquid does not have vapour pressure (non-volatile), so can not disappear after after a while, can continue to obtain antistatic characteristic yet.
In above-mentioned, above-mentioned ionic liquid preferably contains nitrogen salt, contain more than any in sulfosalt or the phosphorous salts.Particularly, above-mentioned ionic liquid preferably comprises more than one the positively charged ion with following general formula (A)～(D) expression.Utilization has these cationic ionic liquids, can obtain the more outstanding material of electrostatic-proof function.
[changing 1]
Figure BDA0000077455830000041
[the R in the formula (A) aThe expression carbonatoms is 4～20 alkyl, can contain heteroatoms, R bAnd R cIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms, wherein, when nitrogen-atoms contains two key, do not have R c];
[the R in the formula (B) dThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R e, R fAnd R gIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms];
[the R in the formula (C) hThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R i, R jAnd R kIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms];
[Z in the formula (D) represents nitrogen, sulphur or phosphorus atom, R l, R m, R nAnd R oIdentical or different, the expression carbonatoms is 1～20 alkyl, can contain heteroatoms, wherein, when Z is sulphur atom, does not have R o].
In addition, as ionic liquid of the present invention, preferably use toluene soluble ion liquid.Contain the binder composition of this toluene soluble ion liquid by use, the binder layer that cross-linking is formed becomes and can reduce the pollution of protected body and static electricity resistance and the good structure of adhesion characteristic when peeling off.
By using above-mentioned toluene soluble ion liquid, can obtain the more outstanding composition of static electricity resistance.The reason that can further improve static electricity resistance by using toluene soluble ion liquid is still indeterminate, but the polarity difference that is speculated as ionic liquid helps the raising of static electricity resistance.
More specifically say, the polarity height of ionic liquid generally speaking, so with respect to non-polar materials such as silicone or fluorine, wettability is relatively poor, on the other hand, the ionic liquid that dissolves in as the toluene of non-polar solvent belongs to the lower liquid of polarity in the middle of ionic liquid, so increase with respect to the wettability of non-polar materials such as silicone or fluorine, even with respect to nonpolar adherend, also can obtain outstanding electrostatic-proof function.
Wherein, toluene solubility characteristic of the present invention is meant and can be dissolved in toluene, more specifically says, is meant that ionic liquid is dissolved in the character in the toluene equably when making 10 weight % toluene solutions of ionic liquid.
And then in the present invention, preferred above-mentioned ionic liquid contains CF 3SO 3 -Negatively charged ion.Contain CF by use 3SO 3 -Anionic ionic liquid, the ionic liquid of the solvability of the relative toluene that has been improved easily (toluene solubility).
In addition, as above-mentioned ionic liquid of the present invention, preferably use alicyclic ionic liquid.By using this alicyclic ionic liquid, can obtain more good static electricity resistance.
Wherein, alicyclic ionic liquid of the present invention is meant the ionic liquid that contains alicyclic structure in the molecular structure, can use the ionic liquid that contains by the alicyclic organic cation composition of following general formula (E) expression particularly.
[changing 2]
Figure BDA0000077455830000061
[the R in the formula (E) pThe expression carbonatoms is 4～20 alkyl, can contain heteroatoms, R qAnd R rIdentical or different, expression hydrogen or carbonatoms are 1～10 alkyl, can contain heteroatoms].
In above-mentioned, above-mentioned ionic liquid preferably contains any in tetramethyleneimine positively charged ion and/or the piperidines positively charged ion.Utilization has these cationic ionic liquids, can obtain the more outstanding material of electrostatic-proof function.
In addition, second-order transition temperature Tg is the polymkeric substance below 0 ℃, preferably will have carbonatoms and be in the acrylate of 1～14 alkyl and/or the methacrylic ester more than a kind as (methyl) acrylic polymers of principal constituent.By these (methyl) acrylic polymerss, become well with the balance of the mutual solubility of ionic liquid, also can fully keep adhesion characteristic.
Wherein, (methyl) of the present invention acrylic polymers is meant acrylic polymers and/or methacrylic polymer.
And then the acid number of preferably above-mentioned (methyl) acrylic polymers is below 1.0.Utilize these (methyl) acrylic polymerss, can substantially not have with the bigger acid functional group of the interaction of ionic liquid and do not have to hinder under the situation of the charge neutralization mechanism that forms by aforesaid molecular transposition, show the good anti-static function.In addition, because use (methyl) acrylic polymers of the alkyl with particular carbon atomicity, so also good with the mutual solubility of ionic liquid, the balance of adhesion characteristic is outstanding, when peeling off, the adherend static electrification can be prevented, and contaminative can be reduced adherend.
Wherein, during acid number of the present invention is meant and the mg number of required potassium hydroxide such as the free fatty acids, resinous acid that contain in the 1g sample, specifically be meant the value of measuring with the method described in the embodiment.
On the other hand, adhesive sheets of the present invention is characterised in that to have the binder layer that contains above-mentioned any binder composition on the single or double of supporter.In adhesive sheets of the present invention,, can prevent adhesive sheet static electrification when peeling off, and can become the adhesive sheets that can reduce the contaminative of adherend owing to used the binder composition of the present invention that can play aforesaid action effect.
In addition, when being that (methyl) acrylic polymers below 1.0 is when the base polymer with acid number, owing to used the binder composition of the present invention that can play aforesaid action effect, so can prevent adherend static electrification when peeling off, and can become the adhesive sheets that can reduce to the contaminative of adherend.
In addition, above-mentioned supporter preferably possesses the plastics film of having implemented the anti-electrostatic processing.Handle by plastics film is implemented anti-electrostatic, can further improve static electricity resistance.In addition, when with acid number be (methyl) acrylic polymers below 1.0 when the matrix compounds, can make adherend peeled off static voltage in ± 0.5kV.
On the other hand, surface protective film of the present invention is characterised in that to have the binder layer that contains above-mentioned any binder composition on the single or double of supporter.In surface protective film of the present invention; owing to used the binder composition of the present invention that can play aforesaid action effect; surface protective film static electrification when peeling off can be prevented, and the surface protective film that can reduce can be become the contaminative of adherend.
And then when binder composition of the present invention was applied to surface protective film, the plastic basis material that is used for protective film was more preferably the material of handling through anti-electrostatic.In surface protective film of the present invention; owing to possess the binder composition that will play aforesaid action effect and carry out the crosslinked binder layer that forms, can to prevent from not implement adherend that anti-electrostatic handles when peeling off charged and reduce adhesive sheets pollution, gluing excellent in reliability to adherend so become.For this reason, particularly charged or pollute and to become in the technical field relevant of very deep problem with e-machine at electrostatic, be very useful as the static electricity resistance surface protective film.
In addition, in adhesion type optics of the present invention,, can not make optics have electrostatic-proof function yet, can under the situation that does not reduce productivity, manufacture a product at an easy rate even do not reset antistatic backing by giving the binder layer electrostatic-proof function.By ionic liquid is used as antistatic agent, can under the situation of not damaging adhesion characteristic, obtain the high binder composition of anti-static effect.
And then adhesion type optics of the present invention contains polaroid, polarizer, brightness improving plate or anti-dazzling under the situation of sheet at this optics, and is effective especially.
Description of drawings
Fig. 1 is illustrated in the signal pie graph that is used to measure the potential measurement portion of peeling off static voltage in example I etc.
Fig. 2 is illustrated in the signal pie graph that is used to measure the potential measurement portion of peeling off static voltage among example II-V etc.
Embodiment
Binder composition of the present invention contain ionic liquid and as the second-order transition temperature Tg of base polymer at the polymkeric substance below 0 ℃.
Wherein, ionic liquid of the present invention is meant the melting salt (ionic compound) that is in a liquid state under the room temperature (25 ℃).
As ionic liquid, preferred use contains nitrogen salt, contains sulfosalt or phosphorous salts, particularly from obtaining the reason of outstanding electrostatic-proof function, the preferred material that constitutes by organic cation composition and anionic component that uses with following general formula (A)～(D) expression.
[changing 3]
Figure BDA0000077455830000081
[the R in the formula (A) aThe expression carbonatoms is 4～20 alkyl, can contain heteroatoms, R bAnd R cIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms, wherein, when nitrogen-atoms contains two key, do not have R c];
[the R in the formula (B) dThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R e, R fAnd R gIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms];
[the R in the formula (C) hThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R i, R jAnd R kIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms];
[Z in the formula (D) represents nitrogen, sulphur or phosphorus atom, R l, R m, R nAnd R oIdentical or different, the expression carbonatoms is 1～20 alkyl, can contain heteroatoms, wherein, when Z is sulphur atom, does not have R o].
Positively charged ion as formula (A) expression, can be exemplified as pyridylium, piperidines positively charged ion, tetramethyleneimine positively charged ion, have the pyrroline skeleton positively charged ion, have the positively charged ion of pyrrole skeleton etc.
As concrete example, can list 1-ethylpyridine positively charged ion, 1-butyl-pyridinium positively charged ion, 1-hexyl pyridylium, 1-butyl-3-picoline positively charged ion, 1-butyl-4-picoline positively charged ion, 1-hexyl-3-picoline positively charged ion, 1-butyl-3,4-lutidine positively charged ion, 1,1-dimethyl pyrrolidine positively charged ion, 1-ethyl-1-crassitude positively charged ion, 1-methyl isophthalic acid-propyl pyrrole alkane positively charged ion, 2-methyl isophthalic acid-pyrroline positively charged ion, 1-ethyl-2-phenylindone positively charged ion, 1,2-dimethyl indole positively charged ion, 1-ethyl carbazole positively charged ion.
Positively charged ion as with formula (B) expression can be exemplified as imidazoles (イ ミ ダ ゾ リ ウ system) positively charged ion, tetrahydropyrimidine positively charged ion, dihydro-pyrimidin positively charged ion etc.
As object lesson, can be exemplified as 1,3-methylimidazole positively charged ion, 1,3-diethyl glyoxaline cation, 1-ethyl-3-Methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-hexyl-3-Methylimidazole positively charged ion, 1-octyl group-3-Methylimidazole positively charged ion, 1-decyl-3-Methylimidazole positively charged ion, 1-dodecyl-3-Methylimidazole positively charged ion, 1-tetradecyl-3-Methylimidazole positively charged ion, 1,2-dimethyl-3-propyl imidazole positively charged ion, 1-ethyl-2,3-methylimidazole positively charged ion, 1-butyl-2,3-methylimidazole positively charged ion, 1-hexyl-2,3-methylimidazole positively charged ion, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidine positively charged ion, 1,2,3-trimethylammonium-1,4,5,6-tetrahydropyrimidine positively charged ion, 1,2,3,4-tetramethyl--1,4,5,6-tetrahydropyrimidine positively charged ion, 1,2,3,5-tetramethyl--1,4,5,6-tetrahydropyrimidine positively charged ion, 1,3-dimethyl-1,4-dihydro-pyrimidin positively charged ion, 1,3-dimethyl-1,6-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-1,4-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-1,6-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--1,4-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--1,6-dihydro-pyrimidin positively charged ion etc.
Positively charged ion as with formula (C) expression can be exemplified as pyrazoles positively charged ion, pyrazoline positively charged ion etc.
As object lesson, can be exemplified as 1-methylpyrazole positively charged ion, 3-methylpyrazole positively charged ion, 1-ethyl-2-methylpyrazole cation moiety.
As positively charged ion with formula (D) expression, the positively charged ion that the part that can be exemplified as tetraalkylammonium cation, trialkyl sulfonium cation, Si Wan Ji phosphonium cation, abovementioned alkyl is replaced by alkenyl, alkoxyl group and then epoxy group(ing) etc.
As object lesson, can be exemplified as tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, the TBuA positively charged ion, the four pentyl ammonium cation, the tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, triethyl ammonium methyl positively charged ion, tributyl ethyl ammonium positively charged ion, trimethylammonium decyl ammonium cation, the tricaprylmethylammonium positively charged ion, three amyl group butyl ammonium cations, three hexyl methyl ammonium cations, three hexyl amyl group ammonium cations, three heptyl ammonium methyl positively charged ions, three amyl group butyl ammonium cations, three heptyl hexyl ammonium cations, dimethyl dihexyl ammonium cation, dipropyl dihexyl ammonium cation, heptyl dimethyl hexyl ammonium cation, N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium cation, glycidyl trimethyl ammonium positively charged ion, the diallyl dimethyl ammonium positively charged ion, N, N-dimethyl-N, N-dipropylammonium positively charged ion, N, N-dimethyl-N, N-dihexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation, N, N-dimethyl-N-ethyl-N-propyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl-N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N-heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium cation, N, N-dimethyl-N-propyl group-N-butyl ammonium cation, N, N-dimethyl-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group-N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-dimethyl-N-butyl-N-heptyl ammonium cation, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, trimethylammonium heptyl ammonium cation, N, N-diethyl-N-methyl-N-propyl ammonium positively charged ion, N, N-diethyl-N-methyl-N-amyl group ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl group-N-amyl group ammonium cation, triethyl ammonium methyl positively charged ion, triethyl propyl ammonium positively charged ion, triethyl amyl group ammonium cation, triethyl heptyl ammonium cation, N, N-dipropyl-N-methyl-N-ethyl ammonium positively charged ion, N, N-dipropyl-N-methyl-N-amyl group ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dibutyl-N-methyl-N-amyl group ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation, the tricaprylmethylammonium positively charged ion, N-methyl-N-ethyl-N-propyl group-N-amyl group ammonium cation, the trimethylsulfonium positively charged ion, the triethyl sulfonium cation, the tributyl sulfonium cation, three hexyl sulfonium cations, the diethylmethyl sulfonium cation, dibutyl ethyl sulfonium cation, the dimethyl decyl sulfonium cation, the tetramethyl phosphonium positively charged ion, Si Yi Ji phosphonium cation, the 4-butyl-phosphonium positively charged ion, Si Wu Ji phosphonium cation, Si Ji Ji phosphonium cation, Si Geng Ji phosphonium cation, Si Xin Ji phosphonium cation, triethyl Jia Ji phosphonium cation, tributyl Yi Ji phosphonium cation, trimethylammonium Gui Ji phosphonium cation, diallyl dimethyl ammonium positively charged ion etc.
Wherein, the preferred tetramethylammonium cation that uses, tetraethylammonium cation, tetrapropylammonium cation, the TBuA positively charged ion, the four pentyl ammonium cation, the tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, triethyl ammonium methyl positively charged ion, tributyl ethyl ammonium positively charged ion, trimethylammonium decyl ammonium cation, the tricaprylmethylammonium positively charged ion, three amyl group butyl ammonium cations, three hexyl methyl ammonium cations, three hexyl amyl group ammonium cations, three heptyl ammonium methyl positively charged ions, three amyl group butyl ammonium cations, three heptyl hexyl ammonium cations, dimethyl dihexyl ammonium cation, dipropyl dihexyl ammonium cation, heptyl dimethyl hexyl ammonium cation, N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium cation, glycidyl trimethyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-propyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl-N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium cation, N, N dimethyl-N-propyl group-N-butyl ammonium cation, N, N-dimethyl-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group-N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-dimethyl-N-butyl-N-heptyl ammonium cation, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, trimethylammonium heptyl ammonium cation, N, N-diethyl-N-methyl-N-propyl ammonium positively charged ion, N, N-diethyl-N-methyl-N-amyl group ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl group-N-amyl group ammonium cation, triethyl ammonium methyl positively charged ion, triethyl propyl ammonium positively charged ion, triethyl amyl group ammonium cation, triethyl heptyl ammonium cation, N, N-dipropyl-N-methyl-N-ethyl ammonium positively charged ion, N, N-dipropyl-N-methyl-N-amyl group ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dibutyl-N-methyl-N-amyl group ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation, the tricaprylmethylammonium positively charged ion, N-methyl-N-ethyl-N-propyl group-asymmetrical tetraalkylammonium cation such as N-amyl group ammonium cation, the trimethylsulfonium positively charged ion, the triethyl sulfonium cation, the tributyl sulfonium cation, three hexyl sulfonium cations, the diethylmethyl sulfonium cation, dibutyl ethyl sulfonium cation, trialkyl sulfonium cations such as dimethyl decyl sulfonium cation, the tetramethyl phosphonium positively charged ion, Si Yi Ji phosphonium cation, the 4-butyl-phosphonium positively charged ion, Si Wu Ji phosphonium cation, Si Ji Ji phosphonium cation, Si Geng Ji phosphonium cation, Si Xin Ji phosphonium cation, triethyl Jia Ji phosphonium cation, tributyl Yi Ji phosphonium cation, tributyl Yi Ji phosphonium cation, asymmetrical Si Wan Ji phosphonium cations such as trimethylammonium Gui Ji phosphonium cation, diallyl dimethyl ammonium positively charged ion etc.
On the other hand, as anionic component,, then be not particularly limited if can become ionic liquid.Specifically, can use as Cl -, Br -, I -, AlCl 4 -, Al 2Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3COO -, CF 3COO -, CH 3SO 3 -, CF 3SO 3 -, (CF 3SO 2) 2N -, (CF 3SO 2) 3C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2N -, C 4F 9SO 3 -, (C 2F 5SO 2) 2N -, C 3F 7COO -, (CF 3SO 2) (CF 3CO) N -Deng.Wherein, the anionic component that particularly contains fluorine atom can obtain low-melting ionic compound, so preferred the use.In addition, CF 3SO 3 -Negatively charged ion has improved easily to the solvability of toluene (toluene solubility) ionic liquid, so preferred the use.
As being used for ionic liquid of the present invention, can from the combination of above-mentioned cation constituent and anionic component, suitably select to use.
Can be enumerated as 1-butyl-pyridinium tetrafluoro and close borate, 1-butyl-pyridinium hexafluoro closes phosphoric acid salt, 1-butyl-3-picoline tetrafluoro closes borate, 1-butyl-3-picoline trifluoro-methanyl sulfonate, two (trifluoromethane sulphonyl) imines of 1-butyl-3-picoline, two (pentafluoride ethane sulphonyl) imines of 1-butyl-3-picoline, 1-hexyl pyridine tetrafluoro closes borate, 2-methyl isophthalic acid-pyrroline tetrafluoro closes borate, 1-ethyl-2-phenylindone tetrafluoro closes borate, 1,2-dimethyl indole tetrafluoro closes borate, 1-ethyl carbazole tetrafluoro closes borate, 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-N-Methylimidazoleacetic salt, 1-ethyl-3-Methylimidazole trifluoroacetate, 1-ethyl-3-Methylimidazole hyptafluorobutyric acid salt, 1-ethyl-3-Methylimidazole trifluoro-methanyl sulfonate, 1-ethyl-3-Methylimidazole perfluorinated butane sulfonate, 1-ethyl-3-Methylimidazole DICYANAMIDE, two (trifluoromethane sulphonyl) imines of 1-ethyl-3-Methylimidazole, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-3-Methylimidazole, 1-ethyl-3-Methylimidazole three (trifluoromethane sulphonyl) imines, 1-butyl-3-Methylimidazole tetrafluoro closes borate, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole trifluoroacetate, 1-butyl-3-Methylimidazole five fluorine butyratess, 1-butyl-3-Methylimidazole trifluoro-methanyl sulfonate, 1-butyl-3-Methylimidazole perfluorinated butane sulfonate, two (trifluoromethane sulphonyl) imines of 1-butyl-3-Methylimidazole, 1-hexyl-3-Methylimidazole bromide, 1-hexyl-3-Methylimidazole muriate, 1-hexyl-3-Methylimidazole tetrafluoro closes borate, 1-hexyl-3-Methylimidazole hexafluorophosphate, 1-hexyl-3-Methylimidazole trifluoro-methanyl sulfonate, 1-octyl group-3-Methylimidazole tetrafluoro closes borate, 1-octyl group-3-Methylimidazole hexafluorophosphate, 1-hexyl-2,3-methylimidazole tetrafluoro closes borate, 1, two (trifluoromethane sulphonyl) imines of 2-dimethyl-3-propyl imidazole, 1-methylpyrazole tetrafluoro closes borate, 3-methylpyrazole tetrafluoro closes borate, two (trifluoromethane sulphonyl) imines of tetrahexyl ammonium, N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoro closes borate, N, two (trifluoromethane sulphonyl) imines of N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium, the diallyl dimethyl ammonium tetrafluoro closes borate, the diallyl dimethyl ammonium trifluoro-methanyl sulfonate, two (trifluoromethane sulphonyl) imines of diallyl dimethyl ammonium, two (pentafluoride ethane sulphonyl) imines of diallyl dimethyl ammonium, glycidyl trimethyl ammonium trifluoro-methanyl sulfonate, two (trifluoromethane sulphonyl) imines of glycidyl trimethyl ammonium, two (pentafluoride ethane sulphonyl) imines of glycidyl trimethyl ammonium, 1-butyl-pyridinium (trifluoromethane sulphonyl) trifluoroacetamide, 1-butyl-3-picoline (trifluoromethane sulphonyl) trifluoroacetamide, 1-ethyl-3-Methylimidazole (trifluoromethane sulphonyl) trifluoroacetamide, diallyl dimethyl ammonium (trifluoromethane sulphonyl) trifluoroacetamide, glycidyl trimethyl ammonium (trifluoromethane sulphonyl) trifluoroacetamide, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-propyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-butyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-amyl group ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-hexyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-ethyl-N-nonyl ammonium, N, N-dimethyl-N, two (trifluoromethane sulphonyl) imines of N-dipropylammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-propyl group-N-butyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-propyl group-N-amyl group ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-propyl group-N-hexyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-propyl group-N-heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-butyl-N-hexyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-butyl-N-heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dimethyl-N-amyl group-N-hexyl ammonium, N, N-dimethyl-N, two (trifluoromethane sulphonyl) imines of N-dihexyl ammonium, two (trifluoromethane sulphonyl) imines of trimethylammonium heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-diethyl-N-methyl-N-propyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-diethyl-N-methyl-N-amyl group ammonium, N, two (trifluoromethane sulphonyl) imines of N-diethyl-N-methyl-N-heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-diethyl-N-propyl group-N-amyl group ammonium, two (trifluoromethane sulphonyl) imines of triethyl propyl ammonium, two (trifluoromethane sulphonyl) imines of triethyl amyl group ammonium, two (trifluoromethane sulphonyl) imines of triethyl heptyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dipropyl-N-methyl-N-ethyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dipropyl-N-methyl-N-amyl group ammonium, N, two (trifluoromethane sulphonyl) imines of N-dipropyl-N-butyl-N-hexyl ammonium, N, N-dipropyl-N, two (trifluoromethane sulphonyl) imines of N-dihexyl ammonium, N, two (trifluoromethane sulphonyl) imines of N-dibutyl-N-methyl-N-amyl group ammonium, N, two (trifluoromethane sulphonyl) imines of N-dibutyl-N-methyl-N-hexyl ammonium, two (trifluoromethane sulphonyl) imines of tricaprylmethylammonium, two (trifluoromethane sulphonyl) imines of N-methyl-N-ethyl-N-propyl group-N-amyl group ammonium etc.
In addition, in the present invention, preferably use toluene soluble ion liquid.Toluene soluble ion liquid can obtain by above-mentioned cation constituent of appropriate combination and anionic component.Wherein, can obtain low-melting ionic compound, so preferred from the anionic component that contains fluorine atom.These cation constituents and anionic component can be distinguished use separately, also can mix more than 2 kinds and use.
As the object lesson of toluene soluble ion liquid, can be exemplified as four pentyl ammonium trifluoro-methanyl sulfonate, tetrahexyl ammonium trifluoro-methanyl sulfonate, four heptyl ammonium trifluoro-methanyl sulfonates etc.
In addition, in the present invention, preferably use alicyclic ionic liquid.As the alicyclic ionic liquid among the present invention, can use the ionic liquid of the alicyclic organic cation composition that contains useful following general formula (E) expression.
[changing 4]
Figure BDA0000077455830000151
[the R in the formula (E) pThe expression carbonatoms is 4～20 alkyl, can contain heteroatoms, R qAnd R rIdentical or different, expression hydrogen or carbonatoms are 1～10 alkyl, can contain heteroatoms].
In the middle of alicyclic organic cation composition, preferably use tetramethyleneimine positively charged ion, piperidines positively charged ion with formula (E) expression.
As concrete example, can be exemplified as 1,1-dimethyl pyrrolidine positively charged ion, 1-methyl-2-ethyl pyrrolidine positively charged ion, 1-methyl isophthalic acid-propyl pyrrole alkane positively charged ion, 1-methyl isophthalic acid-butyl pyrrolidine positively charged ion, 1-methyl-1-pentene base tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-hexyl tetramethyleneimine positively charged ion, 1-methyl isophthalic acid-heptyl tetramethyleneimine positively charged ion, 1-ethyl-1-propyl pyrrole alkane positively charged ion, 1-ethyl-1-butyl pyrrolidine positively charged ion, 1-ethyl-1-amyl group tetramethyleneimine positively charged ion, 1-ethyl-1-hexyl tetramethyleneimine positively charged ion, 1-ethyl-1-heptyl tetramethyleneimine positively charged ion, 1,1-dipropyl tetramethyleneimine positively charged ion, 1-propyl group-1-butyl pyrrolidine positively charged ion, 1,1-dibutyl tetramethyleneimine positively charged ion, 1-propyl group piperidines positively charged ion, 1-amyl piperidine positively charged ion, 1,1-lupetidine positively charged ion, 1-methyl isophthalic acid-ethyl piperidine positively charged ion, 1-methyl isophthalic acid-propyl group piperidines positively charged ion, 1-methyl isophthalic acid-butyl piperidine positively charged ion, 1-methyl-1-pentene phenylpiperidines positively charged ion, 1-methyl isophthalic acid-hexyl piperidines positively charged ion, 1-methyl isophthalic acid-heptyl piperidines positively charged ion, 1-ethyl-1-propyl group piperidines positively charged ion, 1-ethyl-1-butyl piperidine positively charged ion, 1-ethyl-1-amyl piperidine positively charged ion, 1-ethyl-1-hexyl piperidines positively charged ion, 1-ethyl-1-heptyl piperidines positively charged ion, 1,1-dipropyl piperidines positively charged ion, 1-propyl group-1-butyl piperidine positively charged ion, 1,1-dibutyl piperidines positively charged ion etc.
In addition, alicyclic ionic liquid can the above-mentioned cation constituent of appropriate combination and above-mentioned anionic component and obtaining.Wherein, can obtain low-melting ionic compound, so preferred the use especially preferably used (CF from the cation constituent that contains fluorine atom 3SO 2) 2N -, (C 2F 5SO 2) 2N -These cation constituents and anionic component can be distinguished use separately, also can mix more than 2 kinds and use.
As the alicyclic ionic liquid that uses among the present invention, specifically, can be exemplified as 1, two (trifluoromethane sulphonyl) imines of 1-dimethyl pyrrolidine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-ethyl pyrrolidine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-propyl group-tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-butyl pyrrolidine, two (trifluoromethane sulphonyl) imines of 1-methyl-1-pentene base tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-hexyl tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-heptyl tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-propyl pyrrole alkane, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-butyl pyrrolidine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-amyl group tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-hexyl tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-heptyl tetramethyleneimine, 1, two (trifluoromethane sulphonyl) imines of 1-dipropyl tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-propyl group-1-butyl pyrrolidine, 1, two (trifluoromethane sulphonyl) imines of 1-dibutyl tetramethyleneimine, two (trifluoromethane sulphonyl) imines of 1-propyl group piperidines, two (trifluoromethane sulphonyl) imines of 1-amyl piperidine, 1, two (trifluoromethane sulphonyl) imines of 1-lupetidine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-ethyl piperidine, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-propyl group piperidines, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-butyl piperidine, two (trifluoromethane sulphonyl) imines of 1-methyl-1-pentene phenylpiperidines, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-hexyl piperidines, two (trifluoromethane sulphonyl) imines of 1-methyl isophthalic acid-heptyl piperidines, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-propyl group piperidines, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-butyl piperidine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-amyl piperidine, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-hexyl piperidines, two (trifluoromethane sulphonyl) imines of 1-ethyl-1-heptyl piperidines, 1, two (trifluoromethane sulphonyl) imines of 1-dipropyl piperidines, two (trifluoromethane sulphonyl) imines of 1-propyl group-1-butyl piperidine, 1, two (trifluoromethane sulphonyl) imines of 1-dibutyl piperidines, 1, two (pentafluoride ethane sulphonyl) imines of 1-dimethyl pyrrolidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-ethyl pyrrolidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-propyl group-tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-butyl pyrrolidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl-1-pentene base tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-hexyl tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-heptyl tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-propyl pyrrole alkane, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-butyl pyrrolidine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-amyl group tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-hexyl tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-heptyl tetramethyleneimine, 1, two (pentafluoride ethane sulphonyl) imines of 1-dipropyl tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-propyl group-1-butyl pyrrolidine, 1, two (pentafluoride ethane sulphonyl) imines of 1-dibutyl tetramethyleneimine, two (pentafluoride ethane sulphonyl) imines of 1-propyl group piperidines, two (pentafluoride ethane sulphonyl) imines of 1-amyl piperidine, 1, two (pentafluoride ethane sulphonyl) imines of 1-lupetidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-ethyl piperidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-propyl group piperidines, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-butyl piperidine, two (pentafluoride ethane sulphonyl) imines of 1-methyl-1-pentene phenylpiperidines, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-hexyl piperidines, two (pentafluoride ethane sulphonyl) imines of 1-methyl isophthalic acid-heptyl piperidines, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-propyl group piperidines, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-butyl piperidine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-amyl piperidine, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-hexyl piperidines, two (pentafluoride ethane sulphonyl) imines of 1-ethyl-1-heptyl piperidines, two (pentafluoride ethane sulphonyl) imines of 1-propyl group-1-butyl piperidine, 1, two (pentafluoride ethane sulphonyl) imines of 1-dipropyl piperidines, 1, two (pentafluoride ethane sulphonyl) imines of 1-dibutyl piperidines etc.
Aforesaid liquid can use commercially available material, also can be synthetic material as described below.
Synthetic method as ionic liquid, as long as can obtain object ion liquid, then be not particularly limited, but in general, halogenide method, hydroxide process, acid esters method, coordination compound forming method and neutralisation etc. as adopting document " the up-to-date trend of ionic liquid-research and development and future-" (CMC publication and distribution) to be put down in writing.
Be that example is represented synthetic methods such as halogenide method, hydroxide process, acid esters method, coordination compound forming method and neutralisation to contain nitrogen salt below, but other contain other ionic liquids such as sulfosalt, phosphorous salts and also can obtain by identical method.
The halogenide method is the method for being undertaken by the reaction shown in following formula (1)～(3).At first, tertiary amine and haloalkane are reacted and obtain halogenide (reaction formula (1) as halogen, uses chlorine, bromine, iodine).Make the halogenide that obtains with have as the acid (HA) of the anion structure (A-) of the ionic liquid of target or salt (MA, M be ammonium, lithium, sodium, potassium etc. can with the salifiable positively charged ion of target negatively charged ion shape) react, obtain object ion liquid (R 4NA).
[changing 5]
(1)R 3N+RX→R 4NX(X：Cl，Br，I)
(2)R 4NX+HA→R 4N?A+HX
(3) R 4NX+MA → R 4NA+MX (M:NH 4, Li, Na, K, Ag etc.)
Hydroxide process is the method for being undertaken by the reaction shown in (4)～(8).At first, by halogenide (R 4NX) by ion exchange membrane electrolysis (reaction formula (4)), OH type ion-exchange-resin process (reaction formula (5)) or with silver suboxide (Ag 2O) reaction (reaction formula (6)) and obtain oxyhydroxide (R 4NOH) (, use chlorine, bromine, iodine) as halogen.Use the reaction of reaction formula (7)～(8), similarly obtain object ion liquid (R by oxyhydroxide that obtains and above-mentioned halogenide method 4NA).
[changing 6]
(4)R 4NX+H 2O→R 4NOH+1/2H 2+1/2X 2(X：Cl，B?r，I)
(5) R 4NX+P-OH → R 4NOH+P-X (P-OH:OH type ion exchange resin)
(6)R 4NX+1/2Ag 2O+1/2H 2O→R 4NOH+AgX
(7)R 4NOH+HA→R 4NA+HX
(8) R 4NOH+MA → R 4NA+MX (M:NH 4, LI, Na, K, Ag etc.)
The acid esters method is the method for being undertaken by the reaction shown in (9)～(11).At first, make tertiary amine (R 3N) and acid esters react and obtain the acid esters thing.(reaction formula 9, as acid esters, can use the ester of mineral acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, carbonic acid, or organic acid esters such as methylsulfonic acid, methyl-phosphorous acid, formic acid etc.) use the reaction of reaction formula (10)～(11), similarly obtain object ion liquid (R by acid esters thing that obtains and above-mentioned halogenide method 4NA).In addition, by using methyl trifluoro methane sulfonates, methyl trifluoro acetate etc., can directly obtain ionic liquid as acid esters.
[changing 7]
(OY:
Figure BDA0000077455830000191
Deng)
(9)R 3N+ROY→R 4NOY
(10)R 4NOY+HA→RNA+HOY
(OY:
Figure BDA0000077455830000192
Situation under,
Figure BDA0000077455830000193
)
(11) R 4NOY+MA → R 4NA+MOY (M:NH 4, Li, Na, K, Ag etc.)
The coordination compound forming method is the method for being undertaken by the reaction shown in (12)～(15).At first, make the halogenide (R of quaternary ammonium 4NX), the oxyhydroxide (R of quaternary ammonium 4NOH), the carbonic acid carboxylate (R of quaternary ammonium 4NOCO 2CH 3) wait and hydrogen fluoride (HF) or Neutral ammonium fluoride (NH 4F) react and obtain fluoridizing quaternary ammonium salt.(reaction formula (12)～(14)) make obtain fluoridize quaternary ammonium salt and BF 3, AlF 3, PF 5, ASF 5, SbF 5, NbF 5, TaF 5Carry out coordination compound formation reaction in fluorochemical, can obtain ionic liquid thus.(reaction formula (15))
[changing 8]
(12)R 4NX+HF→R 4NF+HX (X：Cl，·Br，I)
(13)R 4NY+HF→R 4NF+HY (Y：OH，OCO 2CH 3)
(14)R 4NY+NH 4F→R 4NF+NH 3+HY (Y：OH，OCO 2CH 3)
(15)R 4NF+MF n-1→R 4NMF n
(M F N-1: BF 3, AIF 3, PF 5, ASF 5, SbF 5, NbF 6, TaF 5Deng)
Neutralisation is the method for being undertaken by the reaction shown in (16).Can be by tertiary amine and HBF 4, HPF 6, CH 3COOH, CF 3COOH, CF 3SO 3H, (CF 3SO 2) 2NH, (CF 3SO 2) 3CH, (C 2F 5SO 2) 2Organic acids such as NH react and obtain.
[changing 9]
(16) R 3N+HZ → R 3HN+Z -[HZ:HBF 4, HPF 6, CH 3COOH, CF 3COOH, CF 3SO 3H, (CF 3SO 2) 2NH, (CF 3SO 2) 3CH, (C 2F 5S O 2) 2Organic acids such as NH]
Above-mentioned R represents that hydrogen or carbonatoms are 1～20 alkyl, can contain heteroatoms.
The use level of ionic liquid changes with the mutual solubility of employed polymkeric substance and ionic liquid, so can not carry out generally defining, but in general, with respect to base polymer 100 weight parts, preferred 0.01～40 weight part, more preferably 0.03～20 weight part, most preferably 0.05～10 weight part.When less than 0.01 weight part, can't obtain enough antistatic characteristics, when surpassing 40 weight parts, the pollution of adherend there is the trend of increase.
In addition, when using alicyclic ionic liquid, as the use level of ionic liquid, in general, and with respect to base polymer 100 weight parts, preferred 0.01～20 weight part, more preferably 0.03～10 weight part, most preferably 0.05～5 weight part.
In the present invention, as base polymer, can use second-order transition temperature Tg at the polymkeric substance below 0 ℃, preferred Tg is-100～5 ℃, and more preferably Tg is-80～-10 ℃.When second-order transition temperature Tg surpasses 0 ℃,, also be difficult to obtain enough bounding forces even contain ionic liquid.
As this polymkeric substance, can enumerate to have in acrylate that carbonatoms is 1～14 alkyl and/or the methacrylic ester is (methyl) acrylic polymers of principal constituent more than a kind or 2 kinds, natural rubber, styrene isoprene styrene block copolymer (SIS) (SIS segmented copolymer), styrene-butadiene-styrene block copolymer (SBS segmented copolymer), styrene-ethylene butylene-styrene segmented copolymer (SEBS segmented copolymer), styrene butadiene rubbers, polyhutadiene, polyisoprene, polyisobutene, isoprene-isobutylene rubber, neoprene, silicone rubbers etc. are as the normally used polymkeric substance of the polymkeric substance of tackiness agent.
Wherein, consider with the angle of the balance of the mutual solubility of ionic liquid and outstanding adhesion characteristic from can obtaining, preferably use to have to be (methyl) acrylic polymers of principal constituent more than a kind or 2 kinds in acrylate that carbonatoms is 1～14 alkyl and/or the methacrylic ester.
As being (methyl) acrylic polymers of principal constituent more than a kind or 2 kinds in acrylate that carbonatoms is 1～14 alkyl and/or the methacrylic ester to have, can use will contain 50～100 weight % have the monomer more than a kind or 2 kinds in acrylate that carbonatoms is 1～14 alkyl and/or the methacrylic ester { below, (methyl) acrylate is meant acrylate and/or methacrylic ester } be principal constituent, weight-average molecular weight is (methyl) acrylic polymers more than 100,000.
From the balanced perspective of bond properties, preferred its second-order transition temperature Tg of above-mentioned (methyl) acrylic polymers is (usually more than-100 ℃) below 0 ℃.In addition, from same viewpoint, the carbonatoms of alkyl preferred 6～14.
As having the object lesson that carbonatoms is (methyl) acrylate of 1～14 alkyl, can be enumerated as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester, (methyl) vinylformic acid n-tetradecane base ester etc.
Wherein, when being used for surface protective film of the present invention, preferred use as (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester, (methyl) vinylformic acid n-tetradecane base ester etc. have (methyl) acrylate that carbonatoms is 6～14 alkyl.By using by having carbonatoms is (methyl) acrylic polymers that (methyl) acrylate of 6～14 alkyl constitutes, and can easily will control lowlyer to the bounding force of adherend, obtains the outstanding material of releasable.
As other polymerizable monomer composition, can suitably use as containing sulfonic group monomer, phosphorous acidic group monomer, cyano-containing monomer, vinyl esters, aromatic vinyl compounds etc. and can improve cohesive force, stable on heating composition, contain carboxylic monomer, contain the anhydride group monomer, hydroxyl monomer, amide-containing monomer, contain amino monomers, contain the imide monomer, contain the epoxy group(ing) monomer, N-acryloyl morpholine, ethene ethers etc. have and can improve the composition of functional group that adhesive power maybe can play the effect of crosslinkedization starting point.Other composition can be used alone or in combination with two or more kinds.
But, when having (methyl) acrylate of acid functional groups such as carboxyl, sulfonic group, phosphate when use, preferably the acid number with (methyl) acrylic polymers is adjusted to below 29.When the acid number of (methyl) acrylic polymers surpassed 29, antistatic characteristic had the trend of variation.
The adjusting of acid number can be finished by the use level that adjusting has (methyl) acrylate of acid functional group, for example, as (methyl) acrylic polymers with carboxyl, can enumerate and make 2-EHA and vinylformic acid generation copolyreaction generate (methyl) acrylic polymers, at this moment, if with respect to 2-EHA and acrylic acid total amount 100 weight parts, the vinylformic acid amount is adjusted to below 3.7 weight parts, then can satisfies the value of above-mentioned acid number.
As containing the sulfonic group monomer, can be exemplified as styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulfo group propyl ester, (methyl) acryloxy naphthene sulfonic acid, sodium vinyl sulfonate etc.
As phosphorous acidic group monomer, can be exemplified as 2-hydroxyethyl acryloyl phosphoric acid ester.
As the cyano-containing monomer, can be exemplified as vinyl cyanide, methacrylonitrile.
As vinyl esters, can be exemplified as vinyl acetate, propionate, vinyl laurate etc.
As the aromatic vinyl compounds, can be exemplified as vinylbenzene, chloro-styrene, 1-chloro-4-methyl-benzene, alpha-methyl styrene, other substituted phenylethylene etc.
As containing carboxylic monomer, can be exemplified as (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan, iso-crotonic acid etc.
As containing the anhydride group monomer, can be exemplified as maleic anhydride, itaconic anhydride, the above-mentioned acid anhydrides that contains carboxylic monomer etc.
As the hydroxyl monomer, can be exemplified as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxyl lauryl, vinylformic acid (4-methylol cyclohexyl) methyl esters, N-methylol (methyl) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl Vinyl Ether, 4-hydroxyl butyl vinyl ether, diglycol monotertiary Vinyl Ether etc.
As the amide-containing monomer, can be exemplified as acrylamide, Methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N, N-DMAA, N, N-dimethylmethacryl amide, N, N-diethyl acrylamide, N, N-diethylmethyl acrylamide, N, N '-methylene-bisacrylamide, N, N dimethylamine base propyl group acrylamide, N, N dimethylamine base propyl methyl acid amides, diacetone acrylamide etc.
As containing amino monomers, can be exemplified as (methyl) vinylformic acid ammonia ethyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) acryloyl morpholine etc.
As containing the imide monomer, can be exemplified as cyclohexyl maleimide, sec.-propyl maleimide, N-cyclohexyl maleimide, clothing health imide etc.
As containing the epoxy group(ing) monomer, can be exemplified as (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester, glycidyl allyl ether etc.
As the ethene ethers, can be exemplified as ethylene methacrylic ether, ethyl vinyl ether, isobutyl vinyl ether etc.
In addition, the acid number of above-mentioned (methyl) acrylic polymers is preferably below 1.0, more preferably below 0.8, and most preferably 0.0.When acid number is 1.0 when following, have with the quantitative change of the interactional acid functional group of ionic liquid fewly, have more infallible static electricity resistance.The adjusting of the acid number of acrylic polymers can have the monomeric usage quantity of carboxyl or sulfonate group or not use this monomer to carry out by minimizing.
When the acid number of acrylic polymers is 1.0 when following,,, just can use if having the acrylate of carboxyl or sulfonate group and/or the composition beyond the methacrylic ester as other compositions that constitute acrylic polymers with being not particularly limited.Wherein, consider that preferred hydroxyl monomer especially preferably has the acrylate and/or the methacrylic ester of hydroxyl from can easily controlling crosslinked angle.
In addition, when the acid number with acrylic polymers is adjusted to 1.0 when following, the monomeric usage quantity of above-mentioned hydroxyl preferably accounts for 0.5～10 weight % in constituting monomer component, more preferably 1～8 weight %.
Other above-mentioned polymerizable monomer compositions can use separately, also can mix more than 2 kinds and use, but content as a whole, total formation unit 100 weight parts with respect to (methyl) acrylic polymers, the polymerizable monomer composition is preferably 0～49 weight part, more preferably 0.1～45 weight part, preferred especially 3～35 weight parts.By using other above-mentioned polymerizable monomer compositions, can suitably regulate and ionic liquid between good interaction and good tackiness.
(methyl) of the present invention acrylic polymers can obtain by the normally used polymerization process of synthetic method of conduct (methyl) acrylic polymerss such as solution polymerization, letex polymerization, mass polymerization, suspension polymerization.In addition, the polymkeric substance that obtains can be any in random copolymers, segmented copolymer, the graft copolymer etc.
Binder composition of the present invention, by suitable crosslinked base polymer, (methyl) acrylic polymers particularly, and then can obtain the outstanding adhesive sheets of thermotolerance.As the concrete gimmick of cross-linking method, have add that isocyanate compound, epoxy compounds, trimeric cyanamide resinoid, nitrogen heterocycle propane compound etc. contain can be with the compound of the group of the reactions such as carboxyl, hydroxyl, amino, amide group that contain as suitable crosslinkedization basic point in (methyl) acrylic polymers and make the method for the what is called use linking agent that they react.Wherein, from the main viewpoint that obtains the cohesive force of appropriateness, especially preferably use isocyanate compound or epoxy compounds.These compounds can use separately, also can mix more than 2 kinds and use.
Wherein, as isocyanate compound, can enumerate aromatic isocyanates such as toluene support vulcabond, xylylene isocyanic ester, alicyclic isocyanates such as isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate etc.
More specifically say, as isocyanic ester, can be exemplified as the butylidene vulcabond, lower aliphatic polymeric polyisocyanate classes such as hexamethylene diisocyanate, the cyclopentylidene vulcabond, the cyclohexylidene vulcabond, alicyclic isocyanate classes such as isophorone diisocyanate, 2,4-toluene support vulcabond, 4,4 '-diphenylmethanediisocyanate, aromatic diisocyanate classes such as xylylene vulcabond, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system, trade(brand)name Coronate L), TriMethylolPropane(TMP)/hexamethylene diisocyanate 3 aggressiveness affixtures (Japanese polyurethane industry system, trade(brand)name Coronate HL), the isocyanuric acid ester body of hexamethylene diisocyanate isocyanate addition products such as (Japanese polyurethane industry system, trade(brand)name Coronate HX) etc.These isocyanate compounds can use separately, also can mix more than 2 kinds and use.
As epoxy compounds, can be exemplified as N, N, N ', N '-four glycidyl group-m-xylene diamine (Mitsubishi's gas chemistry system, trade(brand)name TETRAD-X), 1, two (N, N-diglycidyl amino methyl) hexanaphthenes of 3-(Mitsubishi's gas chemistry system, trade(brand)name TETRAD-C) etc.These compounds can use separately, also can mix more than 2 kinds and use.
As the trimeric cyanamide resinoid, can be exemplified as hexamethylolmelamine etc.
As aziridine derivative, can be exemplified as trade(brand)name HDU, trade(brand)name TAZM as commercially available product, trade(brand)name TAZO (above be mutual pharmaceutical worker's system) etc.These compounds can use separately, also can mix more than 2 kinds and use.
The usage quantity of these linking agents can be according to suiting to select with the balance of crosslinked (methyl) acrylic polymers of needs and as the use of adhesive sheet.For the cohesive force of utilizing acryloid cement obtains sufficient thermotolerance, with respect to above-mentioned (methyl) acrylic polymers 100 weight parts, preferably contain 0.01～15 weight part usually, more preferably contain 0.5～10 weight part.When content is less than 0.01 weight part, can not utilize linking agent full cross-linked, the cohesive force of binder composition reduces, and also can't obtain enough thermotolerances sometimes, in addition, may become the residual reason of glue.On the other hand, when content surpassed 15 weight parts, the cohesive force of polymkeric substance increased, and mobile the reduction is abundant inadequately to the wettability of adherend, may become the reason of being peeled off.
In addition, also can be used as the polyfunctional monomer that substantial linking agent adds the active unsaturated link(age) of radioactive rays that has more than 2, and make it crosslinked by radioactive rays etc.
As polyfunctional monomer, can use the polyfunctional monomer composition of radioactive rays active group more than a kind or 2 kinds that under radiation exposure, can carry out crosslinking Treatment (curing) of the vinyl that has more than 2, acryl, methacryloyl, vinyl benzyl and so on the radioactive rays unsaturated link(age) more than 2.Wherein, the preferred usually active unsaturated link(age) of radioactive rays that uses is at the compound below 10.The polyfunctional monomer that also two or more kinds may be used.
Object lesson as polyfunctional monomer, can be exemplified as ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Vinylstyrene, N, N '-methylene-bisacrylamide etc.
The usage quantity of polyfunctional monomer can be according to the balance of crosslinked (methyl) acrylic polymers of needs, suit to select as the use of adhesive sheet.For the cohesive force by acryloid cement obtains sufficient thermotolerance, with respect to (methyl) acrylic polymers 100 weight parts, preferably cooperate usually with 0.1～30 weight part.In addition, from the viewpoint of flexibility, tackiness, with respect to (methyl) acrylic polymers 100 weight parts, more preferably to cooperate below 10 weight parts.
As radioactive rays, can be exemplified as ultraviolet ray, laser, α line, β line, γ line, X ray, electron rays etc., but from controlled, the fine or not degree of operability, the viewpoint of composition, preferred use ultraviolet ray.More preferably use the ultraviolet ray of wavelength 200～400nm.Can use suitable light sources such as high voltage mercury lamp, microwave-excitation type lamp, luminescent lamp to shine when adopting ultraviolet ray.Wherein, when ultraviolet ray is used as radioactive rays, in the acryloid cement layer, add Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, can be according to the kind of radioactive rays activeconstituents, use can become this polyreaction safety fuse, irradiation can generate free radical or cationic material after the suitable wavelength ultraviolet ray.
As the optical free radical polymerization starter; can be exemplified as bitter almond oil camphor; benzoin methyl ether; ethoxybenzoin; methyl o-benzoylbenzoate-to ethoxybenzoin; benzoin iso-propylether; bitter almond oil camphor classes such as Alpha-Methyl bitter almond oil camphor; benzyl dimethyl ketal; Trichloroacetophenon; 2; the 2-diethoxy acetophenone; acetophenones such as 1-hydroxy-cyclohexyl benzophenone; 2-hydroxy-2-methyl Propiophenone; 2-hydroxyl-4 '-sec.-propyl-phenylpropyl alcohol ketones such as 2-methyl phenyl ketone; benzophenone; the methyldiphenyl ketone; to chlorobenzophenone; to benzophenones such as dimethylin benzophenone; the 2-clopenthixal ketone; 2-ethyl thioxanthone; thioxanthene ketones such as 2-isopropyl thioxanthone; two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; (2; 4; the 6-trimethylbenzoyl)-(oxyethyl group)-acylphosphine oxide classes such as phenyl phosphine oxide; benzil, dibenzosuberone, α-acyl group oxime ester etc.
As the light cationic polymerization initiators, can be exemplified as salt such as aromatic series diazonium salt, aromatic series salt compounded of iodine, aromatic series sulfonium salt, Organometallic complexes class, nitrobenzyl ester, sulfonic acid, phosphoric acid ester, sulfophenylate, diazo naphthoquinone, N-hydroxyl imide base sulfonate etc. such as iron-propadiene coordination compound, two luxuriant titanium (titanocene) coordination compoundes, aryl-silane alcohol-aluminium coordination compound.Also two or more kinds may be used for above-mentioned Photoepolymerizationinitiater initiater.
With respect to (methyl) acrylic polymers 100 weight parts, Photoepolymerizationinitiater initiater is usually at 0.1～10 weight part, preferably cooperate in the scope of 0.2～7 weight part.
And then, also can and with light initiation polymerization auxiliary agents such as amines.As above-mentioned light-initiated auxiliary agent, can enumerate 2-dimethylin ethyl benzoate, dimethylin methyl phenyl ketone, to the dimethylin ethyl benzoate, to dimethylin isoamyl benzoate etc.Above-mentioned photopolymerization causes auxiliary agent, and also two or more kinds may be used.With respect to (methyl) acrylic polymers 100 weight parts, polymerization causes auxiliary agent preferably at 0.05～10 weight part, further cooperate in the scope of 0.1～7 weight part.
And then, be used for the binder composition of adhesive sheet of the present invention, can suitably adding known in the past various additives such as powdery objects such as known in the past various tackifier or surface lubricant, flow agent, oxidation inhibitor, anticorrosive agent, photostabilizer, UV light absorber, polymerization retarder, organosilane coupler, inorganic or organic filler, metal powder, pigment, granular, paper tinsel shape thing according to employed purposes.
On the other hand, binder layer of the present invention carries out crosslinked forming to aforesaid binder composition.In addition, adhesive sheets of the present invention forms binder layer and forms on support film.At this moment, the crosslinked of binder composition carries out after the applying adhesive composition usually, but also the binder layer that is made of the binder composition after crosslinked can be transferred on support film etc.
When adding the Photoepolymerizationinitiater initiater of any composition as described above, after directly being coated in above-mentioned binder composition on the protected body or being coated on the single or double of support base material, can obtain binder layer by rayed.Usually, by with 200～4000mJ/cm 2The light quantity illumination wavelength be that the illumination of 300～400nm is 1～200mW/cm 2Ultraviolet ray, make it that photopolymerization take place and obtain binder layer.
Do not have special requirement for the method that on film, forms binder layer, for example, can remove polymer solvent etc., on support film, form binder layer by the above-mentioned binder composition after drying of coating on support film.Subsequently, the adjusting that can move with the composition of binder layer or the adjusting of crosslinking reaction etc. are that purpose is carried out maintenance.In addition, when making adhesive sheets, can in said composition, add the solvent more than a kind except that polymer solvent again, so that can evenly coating on support film when applying adhesive composition on support film.
In addition, as the formation method of binder layer of the present invention, can use the known method that is used to make adhesive sheets.Specifically, can enumerate the coating of roller coat, photogravure, oppositely coating, roller brush, spraying, pneumatic spread coating, infiltration and curtain formula curtain coating, utilize the extrusion coating method of mold coating machine (die coater) etc.
Adhesive sheets of the present invention is coated on the single or double of the various supporters that are made of porous materials such as plastics films such as polyester film, paper, non-woven fabrics etc. to be formed above-mentioned binder layer and makes slabbing or form such as band shape makes, above-mentioned binder layer is thick 3～100 μ m usually, and preferred thickness is about 5～50 μ m.Particularly under the situation of surface protective film, preferably plastic basis material is used as supporter.
As plastic basis material, if can form sheet or film like, then be not particularly limited, can be exemplified as polyethylene, polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, the polyhutadiene film, poly-methyl pentene film, ethylene-propylene copolymer, ethene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyolefin films such as ethylene-vinyl alcohol copolymer, polyethylene terephthalate, PEN, polyester films such as polybutylene terephthalate, the polyacrylic acid ester film, polyurethane film, polystyrene film, nylon 6, nylon 6,6, polyamide layers such as partially aromatic polyamide, polyvinyl chloride film, the vinyl chloride copolymer film, the polyvinylidene chloride film, polycarbonate film etc.
The thickness of above-mentioned film is generally 5～200 μ m, about preferred 10～100 μ m.
As required, also can implement to utilize the demoulding and the antifouling processing of releasing agent, silicon dioxide powders etc. such as silicone, fluorine class, chain alkyl class or fatty acyl amide to plastic basis material, or easy bonding processing such as acid treatment, alkaline purification, prime treatment, corona treatment, plasma treatment, UV treatment, coating-type, sneak into anti-electrostatics such as type, evaporation type and handle.
In addition, the material more preferably handled of the plastic basis material that is used for surface protective film of the present invention through anti-electrostatic.
Handle as the anti-electrostatic that plastic basis material is implemented, be not particularly limited, can use as the method for antistatic backing being set on the single face of normally used film at least, on plastics film, sneaking into the method for type antistatic agent.
As the method that antistatic backing is set on the single face of film at least, can be exemplified as the static electricity resistance resin that coating is made of antistatic agent and resinous principle, or contain the method for the electroconductive resin of electric conductive polymer, conductive material; Or the method for evaporation or plating conductive material.
As the antistatic agent that in the static electricity resistance resin, contains, can be exemplified as quaternary ammonium salt, pyridinium salt, contain primary, secondary, the cationic antistatic agent of cationic functional groups such as tertiary amine groups, sulfonate, sulfuric acid, phosphonate, phosphate ester salts etc. contain the anionic antistatic agent of anionic property functional group, alkyl betaine and derivative thereof, tetrahydroglyoxaline and derivative thereof, amphoteric such as L-Ala and derivative thereof antistatic agent, amino alcohol and derivative thereof, glycerine and derivative thereof, non-ionic antistatic agent such as polyoxyethylene glycol and derivative thereof, and make above-mentioned have cationic, anionic, the monomer of the ionic conductivity group of amphoteric ion type carries out polymerization or copolymerization and the ionic conduction type polymkeric substance that obtains.These compounds can use separately, can also mix more than 2 kinds and use.
Specifically; as cationic antistatic agent, can be exemplified as styrol copolymer that (methyl) acrylate copolymer that alkyl trimethyl ammonium salt, acyl group acyl (ア シ ロ イ Le) amido propyl trimethyl ammonium methyl-sulfate, alkyl benzyl methyl ammonium salt, acyl group choline chloride 60, polymethyl acrylic acid dimethylin ethyl ester etc. have quaternary ammonium group, polyvinyl benzyltrimethylammon.um muriate etc. have quaternary ammonium group, polydiene propyl-dimethyl ammonium muriate etc. and have diallylamine multipolymer of quaternary ammonium group etc.These compounds can use separately, can also mix more than 2 kinds and use.
As the anionic antistatic agent, can be exemplified as alkylsulfonate, alkylbenzene sulfonate, alkyl sulfuric ester salt, AES salt, alkyl phosphate salt, contain sulfonic styrol copolymer.These compounds can use separately, can also mix more than 2 kinds and use.
As the amphoteric ion type antistatic agent, can be exemplified as alkyl betaine (betaine), alkyl imidazole trimethyl-glycine, carbonyl trimethyl-glycine graft copolymer.These compounds can use separately, can also mix more than 2 kinds and use.
As non-ionic antistatic agent, the multipolymer that can be exemplified as fatty acid alkyl alcohol amide, two (2-hydroxyethyl) alkylamine, polyoxyethylene alkyl amine, glycerin fatty acid ester, polyoxyethylene glycol fatty acid ester, sorbitan-fatty acid ester, polyoxygenated sorbitan-fatty acid ester, polyoxyethylene alkyl phenyl ether, Voranol EP 2001, polyoxyethylene glycol, polyethyleneoxide diamine, constitute by polyethers and polyester and polymeric amide, methoxy poly (ethylene glycol) (methyl) acrylate etc.These compounds can use separately, can also mix more than 2 kinds and use.
As electric conductive polymer, can be exemplified as polyaniline, polypyrrole, Polythiophene etc.These electric conductive polymers can use separately, can also mix more than 2 kinds and use.
As conductive material, can be exemplified as stannic oxide, weisspiessglanz, Indium sesquioxide, Cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold and silver, copper, aluminium, nickel, chromium, titanium, iron, cobalt, cupric iodide and their alloy or mixture.These electric conductive polymers can use separately, can also mix more than 2 kinds and use.
As the resinous principle that is used for static electricity resistance resin and electroconductive resin, can use as resins for universal use such as polyester, acrylic resin, polyvinyl resin, urethane, melamine resin, Resins, epoxy.Wherein, when being the polymer antistatic agent, can not resinous composition.In addition, in the anti-electrostatic resinous principle, also can contain compound, epoxy compounds, isocyanate compounds such as melamine class as linking agent, urea class, oxalic dialdehyde class, acrylic amide through the alcoholization of methylolation or alkyl.
As the formation method of antistatic backing, can enumerate with organic solvent or water equal solvent and dilute coating on plastics film behind above-mentioned static electricity resistance resin, electric conductive polymer, the electroconductive resin, dry this coating liquid and the method that forms.
As the organic solvent that is used to form above-mentioned antistatic backing, can enumerate methylethylketone, acetone, vinyl acetic monomer, tetrahydrofuran (THF), diox, pimelinketone, normal hexane, toluene, dimethylbenzene, methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.These solvents can use separately, can also mix more than 2 kinds and use.
About the coating method in the formation of above-mentioned antistatic backing, can suitably use known coating method, specifically, can be exemplified as the coating of roller coat, photogravure, oppositely coating, roller brush, spraying, pneumatic spread coating, infiltration and curtain formula curtain coating, utilize the extrusion coating method of mold coating machine etc.
The thickness of above-mentioned static electricity resistance resin layer, electric conductive polymer, electroconductive resin is generally 0.01～5 μ m, about preferred 0.03～1 μ m.
Method as the evaporation or the plating of conductive material can be exemplified as vacuum evaporation, sputter, ion plating, chemical vapor deposition, spraying thermolysis, chemical plating, electrochemical plating etc.
The thickness of above-mentioned conductive material layer is generally 20～10000
Figure BDA0000077455830000301
, preferred 50～5000
In addition, as sneaking into the type antistatic agent, can suit to use above-mentioned antistatic agent.
As above-mentioned use level of sneaking into the type antistatic agent,, can below 20 weight %, preferably in the scope of 0.05～10 weight %, use with respect to the gross weight of plastics film.As the method for sneaking into,, just without limits, can use as warming mill, banbury mixers, pressurization kneading machine, twin shaft sand mill etc. so long as above-mentioned antistatic agent can be blended in equably the method for the resin that is used for plastics film.
As required, also can to plastics film implement to utilize silicone, fluorine class, chain alkyl class or or the demoulding and the antifouling processing of the releasing agent of fatty acyl amide, silicon dioxide powder etc., or easy bonding processing such as acid treatment, alkaline purification, prime treatment, corona treatment, plasma treatment, UV treatment.
In case of necessity, in order to protect adhesive face, the barrier sheet (perhaps release liner, stripping film etc.) of can on adhesive surface, fitting in the adhesive sheets of the present invention.Base material as constituting barrier sheet has paper or plastics film, but from the outstanding viewpoint of surface smoothness, preferably uses plastics film.
As this film; so long as can protect the film of above-mentioned binder layer; just be not particularly limited; can be exemplified as polyethylene; polypropylene; poly-1-butylene; poly--4-methyl-1-pentene; ethylene-propylene copolymer; ethene-butene-1 copolymer; ethylene-vinyl acetate copolymer; ethylene-ethyl acrylate copolymer; polyolefin films such as ethylene-vinyl alcohol copolymer; polyethylene terephthalate; PEN; polyester films such as polybutylene terephthalate; the polyacrylic acid ester film; polystyrene film; nylon 6; nylon 6; 6; polyamide layers such as partially aromatic polyamide; polyvinyl chloride film; the polyvinylidene chloride film, polycarbonate film etc.
The thickness of above-mentioned film is generally 5～200 μ m, about preferred 10～100 μ m.Can on the binder layer binding face of above-mentioned film, utilize the releasing agent, silicon dioxide powder etc. of silicone, fluorine class, chain alkyl class or fatty acyl amide and suitably implement releasing agent and handle.
Utilized binder composition of the present invention, binder layer and adhesive sheets can be used for being easy to generate especially electrostatic plastic prod etc.; wherein, especially can be as the surface protective film of optical component surfaces such as the polaroid that in liquid-crystal display etc., uses with protection, wavelength plate, optical compensating film, light diffusing sheet, reflector plate as purpose.
As mentioned above, adhesion type optics of the present invention is, forms on the single or double of optics that thickness is generally 3～200 μ m, the binder layer that contains binder composition that is preferably 10～100 μ m forms.The formation of binder layer is undertaken by directly being coated in the method etc. that method on the optics, transfer printing coating earlier is formed on the layer on other base materials (for example release liner etc.) usually.
Coating formation method as binder layer, can use the known method of the manufacturing that is used for self adhesive tape, specifically, can be exemplified as the coating of roller coat, photogravure, oppositely coating, roller brush, spraying, pneumatic spread coating, infiltration and curtain formula curtain coating, utilize the extrusion coating method of mold coating machine etc.
As optics, can use the member that is used to make various display unit etc., its kind is not particularly limited, but comprises polaroid, polarizer, brightness improving plate or antiglare sheet etc.Wherein, the stacked members that optical material forms more than 2 layers such as duplexer of duplexer, polaroid and the brightness improving plate or the antiglare sheet of the member of optics polaroid that can be stacked and polarizer, polarizer.
For example, use the member that on polariscopic single or double, has transparent protective film usually as polaroid.
Can use various polariscopes as polariscope with being not particularly limited.As polariscope, can be exemplified as on hydrophilic macromolecule films such as polyvinyl alcohol film, the formalized polyvinyl alcohol film of part, the partly-hydrolysed film of ethylene-vinyl acetate copolymer class the film of dichroic substance such as absorption iodine or dichroic dye and unilateral stretching; Polyalkenes oriented films such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol or polyvinyl chloride etc.In these polariscopes, the preferred polariscope that constitutes by dichroic substance such as polyvinyl alcohol film and iodine.These polariscopic thickness are not particularly limited, but are considered as the intensity of film and the uniformity when stretching, preferred 1 μ m～1mm, more preferably 20 μ m～200 μ m.
With the polyvinyl alcohol film with iodine staining after the polariscope that unilateral stretching forms, for example, back draft to 3 to 7 times of raw footage that can dye by the aqueous solution that polyvinyl alcohol be impregnated in iodine are made.As required, but also can impregnated in the aqueous solution of potassiumiodide etc. of boronic acid containing or zinc sulfate, zinc chloride etc.In addition, as required, also can be before dyeing in water, wash polyvinyl alcohol is thin film dipped.By washing polyvinyl alcohol film, in addition dirt and anti on can flush away polyvinyl alcohol film surface, also can prevent non-uniform phenomenons such as stain by making the polyvinyl alcohol films swell.Stretch and both can after with iodine staining, carry out,, perhaps also can after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or potassiumiodide etc.
Be arranged on the material of the transparent protective film on the above-mentioned polariscopic single or double as formation, the preferred excellent material such as the transparency, physical strength, thermostability, covering property of moisture, isotropy of using.Can be exemplified as polyester polymers such as polyethylene terephthalate or PEN; Cellulosic polymer such as secondary cellulose acetate or cellulose triacetate; Acrylic polymerss such as polymethylmethacrylate; Polystyrene or acrylonitritrile-styrene resin styrenic polymers such as (AS resins); Polycarbonate polymer etc.In addition, the example as the polymkeric substance that forms above-mentioned transparent protective film can also be exemplified as polyethylene, polypropylene, have the polyolefin polymers of the polyolefine, ethylene-propylene copolymer and so on of ring-type or norbornylene structure; The polyvinyl chloride-base polymkeric substance; Acylamide polymer such as nylon or aromatic polyamide; The acid imide polymkeric substance; The sulfone base polymer; The polyether sulfone polymkeric substance; Polyether-ether-ketone polymer; The polyphenylene sulfide base polymer; The vinyl alcohol base polymer, the vinylidene chloride base polymer; The polyvinyl butyral acetal base polymer; The aryl nitrone polymkeric substance; The polyoxymethylene base polymer; Epoxide polymer; Perhaps above-mentioned mixture of polymers etc.Transparent protective film can also form the cured layer of the resin of thermohardening types such as acrylic acid or the like, amino formate, propenoic methyl carbamate class, epoxies, silicone, ultraviolet hardening.
In addition, can enumerate the spy and open the polymeric film described in the 2001-343529 communique (WO01/37007), as contain have on (A) side chain replace and/or not the substituted imine base thermoplastic resin and (B) have the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group on the side chain.As concrete example, can enumerate the film of the resin combination that contains the alternating copolymer that constitutes by iso-butylene and N-methyl maleimide and acrylonitritrile-styrene resin.The film that can use extrusion product by resin combination etc. to constitute as film.
Can suitably determine the thickness of protective film, but generally from viewpoints such as operations such as intensity or operability, thin layers, its thickness is about 1～500 μ m.Preferred especially 1～300 μ m, more preferably 5～200 μ m.
In addition, transparent protective film is preferably not painted as far as possible.Therefore; the preferred protective film that uses is to use Rth=[(nx+ny)/2-nz] d is (wherein; nx, ny are the principal refractive indexs in the thin film planar, and nz is the specific refractory power of film thickness direction, and d is a film thickness) phase difference value of the film thickness direction of expression for-90nm～+ film of 75nm.Phase difference value (Rth) by the used thickness direction is-90nm～+ film of 75nm, can almost completely eliminate painted (optical clouration) of the polaroid that causes by protective film.Thickness direction phase difference value (Rth) more preferably-80nm～+ 60nm, preferred especially-70nm～+ 45nm.
From viewpoints such as polarized light characteristic and weather resistance, as cellulosic polymers such as the preferred cellulose triacetates of protective film.Preferred especially cellulose triacetate film.Wherein, when in polariscopic both sides protective film being set, the protective film that is made of the same polymer material can be used in the outside in it, also can use the protective film that is made of different polymer materialss etc.Above-mentioned polariscope and protective film are by adhesions such as water system tackiness agent.As the water system tackiness agent, can illustration isocyanate-based tackiness agent, polyethenol series tackiness agent, gelatin be tackiness agent, ethene base system latex class, aqueous polyurethane, water system polyester etc.
Not having on bonding polariscopic of above-mentioned transparent protective film, can implement hard coat or antireflection processing, anti, with diffusion or anti-dazzle be the processing of purpose.
Implement purpose that hard coat handles and be to prevent the surface distress of polaroid etc., mode that for example can be by the curing tunicle that the additional hardness that is made of suitable uv curing resin such as acrylic acid or the like, silicone, sliding properties etc. are good on the surface of transparent protective film etc. forms.Implementing the purpose that antireflection handles is the outer reflection of light that prevents on the polaroid surface, can finish by forming to wait based in the past antireflective film.In addition, implementing purpose that anti handles is the adhesion that prevents with adjacent layers
In addition; the purpose of implementing non-glare treated is to prevent that outer light from disturbing polaroid to see through the identification etc. of light in the polaroid surface reflection; for example; can give the micro concavo-convex structure to the transparent protective film surface and form by adopting sandblast mode or the asperities mode of embossing processing mode and the suitable modes such as mode that cooperate transparent particulate.As the particulate that in the formation of above-mentioned surperficial micro concavo-convex structure, contains, for example, the transparent particulates such as organic based fine particles that can to use median size be the mineral-type particulate of the had electroconductibility that is made of silicon-dioxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide, Cadmium oxide, weisspiessglanz etc. of 0.5～50 μ m, be made up of crosslinked or uncrosslinked polymkeric substance etc.When forming surperficial micro concavo-convex structure, the usage quantity of particulate is typically about 2～50 weight parts, preferred 5～25 weight parts with respect to the transparent resin of the formation surface micro concavo-convex structure of 100 weight parts.Antiglare layer also can be also used as the diffusion layer (visual angle expanded functionality etc.) that polaroid transmitted light diffusion is enlarged visual angle etc.
Also have, above-mentioned anti-reflection layer, antiblocking layers, diffusion layer and antiglare layer etc. except can being set to transparent protective film self, can also as other optical layers and be arranged with the transparent protective film branch.
For example, make antiglare layer form sheet, or the layer that is formed on the transparent substrate become antiglare layer.Thickness to antiglare layer is not particularly limited, and considers the intensity as sheet material, preferred 1 μ m～1mm.
In addition, as optics of the present invention, can be exemplified as the material that reflector or half transmitting plate, polarizer (comprising 1/2 or 1/4 wavelength plate), viewing angle compensation film, brightness improving film etc. can become the optical layers that is used to form liquid crystal indicator etc.They can be used alone as optics of the present invention, in addition, can be layered on the above-mentioned polaroid when practical application and then use more than 1 layer or 2 layers.
Reflection type polarizer that forms particularly preferably in further stacked reflector or semi-penetration plate on the polaroid or semi-transmission type polaroid, at the further ellipsoidal polarizing plate that forms of laminated phase-difference plate or circular polarizing disk, the wide visual angle polaroid that forms at further stacked viewing angle compensation film on the polaroid or the polaroid that further stacked brightness improving film forms on polaroid on the polaroid.
Reflection type polarizer is the polaroid that the reflecting layer is set on polaroid, be used to form and make from the liquid crystal indicator of reflection of the incident light of identification side (demonstration side) and the type that shows etc., have and to omit the built-in of light sources such as backlight and make advantage such as liquid crystal indicator slimming easily.The formation of reflection type polarizer can be undertaken by the suitable way such as mode that the reflecting layer that is made of metal etc. is set on the single face of polaroid by protective clear layer etc. as required.
As the object lesson of reflection type polarizer, can be exemplified as required by on the single face of the transparent protective film of handling through delustring, set up the paper tinsel formed by reflective metal such as aluminium or vapor-deposited film and formed the polaroid etc. in reflecting layer.In addition, can also be exemplified as by making above-mentioned transparent protective film contain particulate and form surperficial micro concavo-convex structure, and have the reflection type polarizer etc. in the reflecting layer of micro concavo-convex structure thereon.The reflecting layer of above-mentioned micro concavo-convex structure makes incident light diffusion by diffuse-reflectance, prevents that thus directional property and outward appearance are shinny, has the advantage that can suppress the light and shade inequality etc.In addition, the transparent protective film that contains particulate also has when incident light and reflected light thereof see through it the advantage etc. that can further suppress the light and shade inequality by diffusion.The formation in reflecting layer of the micro concavo-convex structure of the surperficial micro concavo-convex structure of reflection transparent protective film, method that for example can be by directly setting up metal on the surface of protective clear layer with suitable modes such as evaporation mode such as vacuum evaporation mode, ion plating mode and sputter mode or plating modes etc. is carried out.
Instead reflector directly is attached to the method on the transparent protective film of above-mentioned polaroid, the reflecting layer can also be set on the suitable film that with this transparent film is benchmark forms uses such as reflector plate.Also have; because the reflecting layer is made up of metal usually; so from the decline of the reflectivity that prevents to cause, and then keep the viewpoint of initial reflectance for a long time and the viewpoint avoiding establishing protective layer in addition waits, preferably cover the type of service of its plane of reflection with transparent protective film or polaroid etc. owing to oxidation.
Also have, in above-mentioned, the semi-transmission type polaroid can come the catoptrical reflecting layer of the semi-transmission types such as semi-transparent semi-reflecting lens of light transmission that makes simultaneously to obtain by making with the reflecting layer.The semi-transmission type polaroid is located at the rear side of liquid crystal cells usually, can form the liquid crystal indicator of following type etc., promptly, in brighter environment, use under the situation of liquid crystal indicator etc., reflection comes from the incident light of identification side (demonstration side) and display image, in darker environment, use the built-in light sources such as backlight at the back side that is built in the semi-transmission type polaroid to come display image.That is to say, the semi-transmission type polaroid is very useful in the formation of liquid crystal indicator of following type etc., promptly, under bright environment, can save the energy that uses light sources such as backlight, under darker environment, also can utilize in the formation of liquid crystal indicator etc. of type of built-in light source use very useful.
Ellipsoidal polarizing plate or the circular polarizing disk that further laminated phase-difference plate on the polaroid is constituted describes below.Rectilinearly polarized light being changed into elliptically polarized light or circularly polarized light, elliptically polarized light or circularly polarized light being changed into rectilinearly polarized light or changed under the situation of polarization direction of rectilinearly polarized light, can use polarizer etc.Particularly, as rectilinearly polarized light being changed into circularly polarized light, circularly polarized light being changed into the polarizer of rectilinearly polarized light, can use so-called 1/4 wavelength plate (being also referred to as λ/4 plates).1/2 wavelength plate (being also referred to as λ/2 plates) is generally used for changing the situation of the polarization direction of rectilinearly polarized light.
Ellipsoidal polarizing plate can be used for following situation etc. effectively, i.e. compensation (preventing) supertwist nematic phase (STN) type liquid crystal indicator painted (blue or yellow) that produce because of the double refraction of liquid crystal layer, thus carry out the above-mentioned painted white black situation that shows that do not have.In addition, it is painted that the polaroid of control three-dimensional refractive index produces in the time of can also compensating (preventing) from the picture of oblique observation liquid crystal indicator, thereby preferred.Circularly polarizing plate for example can be used for effectively to situation of adjusting with the tone of the image of the reflection-type liquid-crystal display device of color display image etc., but also has the function of reflecting of preventing.
As polarizer, can enumerate and macromolecular material is implemented unidirectional or two-way stretch handle the oriented film of the birefringent film that forms, liquid crystalline polymers, the oriented layer of liquid crystalline polymers is supported in polarizer on the film etc.Thickness to polarizer is not particularly limited, and is generally about 20～150 μ m.
As macromolecular material, for example can enumerate polyvinyl alcohol, polyvinyl butyral acetal, poly-ethylene methacrylic ether, the polyacrylic acid hydroxyethyl ester, Natvosol, hydroxypropylcellulose, methylcellulose gum, polycarbonate, polyarylester, polysulfones, polyethylene terephthalate, PEN, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyene propyl group sulfone, polyvinyl alcohol, polymeric amide, polyimide, polyolefine, polyvinyl chloride, cellulosic polymer, norbornene resin, or their two metaclass, the various multipolymers of three metaclass, graft copolymer, mixture etc.These macromolecular materials can wait by stretching becomes orientation thing (oriented film).
As liquid-crystalline polymer, for example can enumerate the backbone chain type of the linearity atomic group (mesogene) that on the main chain of polymkeric substance or side chain, has imported the conjugacy of giving liquid crystal aligning or various polymkeric substance of side chain type etc.Object lesson as the backbone chain type liquid crystal polymkeric substance, can enumerate and have the polymkeric substance that combines the structure of above-mentioned mesogene base on the spacer portion of bendability giving, for example to the polyester liquid-crystalline polymer of row orientation, discoid polymkeric substance or cholesteric polymers etc.Object lesson as the side chain type liquid crystal polymkeric substance, can enumerate following compound etc., promptly, with polysiloxane, polyacrylic ester, polymethacrylate or poly-malonic ester is main chain backbone, and the spacer portion that constitutes by the atomic group by conjugacy as side chain has the polymkeric substance of the mesogene portion that is made of the para-orientation ring-type compound unit of giving to the row orientation.These liquid crystalline polymerss are handled by the following method, promptly, material after carrying out friction treatment, oblique evaporation for the surface that is formed on films such as polyimide on the sheet glass or polyvinyl alcohol on the orientation process face of oxide materials etc., heat-treat after sprawling the solution of liquid-crystalline polymer.Polarizer can be that for example various wavelength plates or the be used to material that compensates the painted or visual angle that the double refraction by liquid crystal layer causes etc. etc. has the material corresponding to the suitable phase differential of application target, also can be stacked more than 2 kinds polarizer and controlled the material of optical characteristics such as phase differential.
Above-mentioned in addition ellipsoidal polarizing plate or reflection-type ellipsoidal polarizing plate are by suitably combination and laminated polarizing sheet or reflection type polarizer and polarizer form.This class ellipsoidal polarizing plate etc. also can form by stacked respectively successively (reflection-type) polaroid and polarizer in the manufacturing processed of liquid crystal indicator, to constitute the combination of (reflection-type) polaroid and polarizer, and as mentioned above, be pre-formed under the situation for optical thin films such as ellipsoidal polarizing plates, because outstanding, therefore has the advantage of the manufacturing efficient that can improve liquid crystal indicator etc. at aspects such as quality of stability and lamination operation.
The viewing angle compensation film is also can make image seem more clearly, be used to enlarge the film at visual angle under the situation of the picture of observing liquid crystal indicator from the direction that tilts a little that is not orthogonal to picture.As this viewing angle compensation polarizer, for example can constitute by the oriented film of polarizer, liquid crystalline polymers etc. or at material of the oriented layer of transparent substrate upper support liquid crystalline polymers etc. etc.Usually be implemented unilateral stretching, had birefringent polymeric film along its face direction as what polarizer used, relative therewith, as the polarizer that is used as the viewing angle compensation film, can use along its face direction be implemented the birefringent polymeric film of having of two-way stretch, the specific refractory power of the may command thickness direction that also has been stretched by unidirectional stretching and along its thickness direction along its face direction have biaxially oriented films such as birefringent polymkeric substance or picture tilted alignment film etc.As the tilted alignment film, for example can enumerate and polymeric film carried out stretch processing under because of the effect of the convergent force that adds thermosetting behind the bonding heat-shrinkable film on the polymeric film or/and the material of shrink process, make material that the liquid crystalline polymers tilted alignment forms etc.As the starting material polymkeric substance of polarizer can use with above-mentioned polarizer in the polymer phase that illustrates with polymkeric substance, can use to prevent that the knowledge that forms based on the phase differential that is caused by liquid crystal cells from recognizing the painted grade that variation was brought at angle or enlarging the suitable polymer blend as purpose such as the good visual angle of identification.
In addition, wait from the viewpoint that reaches the good wide visual angle of identification, can preferably use the optical compensation polarizer of the optical anisotropic layer that constitutes by the tilted alignment layer of the oriented layer of liquid crystalline polymers, particularly discoid liquid crystalline polymers with the cellulose triacetate film support.
Polaroid and the film adhered polaroid that together forms of brightness improving are located at usually the back side one side of liquid crystal cells.The brightness improving film is the film that shows below characteristic, promptly, when by the backlight of liquid crystal indicator etc. or from reflection of rear side etc., when natural light incident is arranged, the rectilinearly polarized light of reflection regulation polarization axle or the circularly polarized light of prescribed direction, and make other light transmissions, therefore brightness improving film and the stacked polaroid that forms of polaroid can be made light incident from light sources such as backlights, and the light that sees through of polarization state is stipulated in acquisition, simultaneously, light beyond the described regulation polarization state can not see through, and is reflected.Be reversed in the light that reflects on this brightness improving pellicular front once more by reflecting layer of being located at its rear side etc., make it to incide once more on the brightness improving film, make its part or all as the light of regulation polarization state and see through, thereby increase the light that sees through the brightness improving film, simultaneously provide the polarized light that is difficult to absorb to polariscope, can be thereby increase in the light quantity of utilization in the demonstration of liquid crystal display image etc., and can improve brightness thus.Promptly, pass polariscope and make under the light incident situation from the rear side of liquid crystal cells with backlight etc. not using the brightness improving film, have light with the inconsistent polarization direction of polariscopic polarization axle and be polarized mirror basically and absorb, thereby can't see through polariscope.That is, though can be different because of employed polariscopic characteristic, about 50% light can be polarized mirror and sponge, and therefore utilizable light quantity will correspondingly reduce in liquid crystal indicator etc., causes the image deepening.Because the brightness improving film carries out following operation repeatedly, promptly, make light not incide on the polariscope with the polarization direction that can be polarized the mirror absorption, but such light is reflected on the brightness improving film, and then finish counter-rotating by reflecting layer of being located at its rear side etc., light is incided on the brightness improving film once more, like this, the brightness improving film only makes in the light of the two reflection and counter-rotating, its polarization direction becomes and can see through by the polarized light of polariscopic polarization direction, provide it to polariscope simultaneously, therefore can in the demonstration of the image of liquid crystal indicator, use the light of backlight etc. effectively, thereby can make picture bright.
Between brightness improving film and above-mentioned reflecting layer etc., also diffuser plate can be set.Towards described reflecting layer etc., set diffuser plate can spread the light that passes through equably by the light of the polarization state of brightness improving film reflection, eliminates polarization state simultaneously and becomes unpolarized state.That is, diffuser plate makes polarized light return to original natural light state.With this unpolarized state light directive reflecting layer that is the natural light state etc., after reflections such as reflecting layer,, carry out so repeatedly once more by diffuser plate and incide on the brightness improving film.Make polarized light return to the diffuser plate of original natural light state by between brightness improving film and above-mentioned reflecting layer etc., being provided with thus, can be in the brightness of keeping display frame, reduce the inequality of the brightness of display frame, thereby even and bright picture can be provided.By this diffuser plate is set, can suitably increase the repeated reflection number of times of first incident light, and utilize the diffusion function of diffuser plate, bright uniformly display frame can be provided.
As above-mentioned brightness improving film, for example can use: the demonstration of thin-film multilayer duplexer that dielectric multilayer film or specific refractory power anisotropy are different and so on send as an envoy to the rectilinearly polarized light of regulation polarization axle see through and reflect the characteristic of other light film, cholesteric liquid crystal polymer alignment films or in the film substrate upper support the demonstrating any circularly polarized light reflection that will be in left-handed or the dextrorotation of film and so on of this aligned liquid-crystal layer and film that the film etc. of the characteristic of other light transmissions is suited.
Therefore, make the brightness improving film of the type that the rectilinearly polarized light of above-mentioned regulation polarization axle sees through by utilization, make this see through light and directly incide on the polaroid, can when suppressing the absorption loss that causes by polaroid, light be seen through effectively along the direction consistent with polarization axle.On the other hand, utilize the brightness improving film that makes the type that circularly polarized light sees through of cholesteric and so on, though light is incided on the polariscope, but, consider from suppressing the absorption loss this point, preferably this circularly polarized light carry out rectilinearly polarized lightization, reenter afterwards and be mapped on the polaroid by polarizer.And, by using 1/4 wavelength plate, circularly polarized light can be transformed to rectilinearly polarized light as this polarizer.
In broad wavelength regions such as visible region, can play the polarizer of 1/4 wavelength plate effect, for example can utilize following mode to obtain, that is, the phase separation layer that will play the phase separation layer of 1/4 wavelength plate effect with respect to the light luminous energy of 550nm wavelength and show other the phase difference characteristics phase separation layer that for example can play 1/2 wavelength plate effect carries out eclipsed mode etc.So the polarizer that is disposed between polaroid and the brightness improving film can be made of the phase separation layer more than 1 layer or 2 layers.
Also have, with regard to cholesteric, also can make up the material of different reflection wavelengths, constitute overlapping arrangement more than 2 layers or 3 layers, obtain member thus, thereby can obtain the circularly polarized light that sees through of broad wavelength region based on this at the wavelength region internal reflection circularly polarized light of broads such as visible region.
In addition, polaroid is as above-mentioned polarized light divergence type polaroid, can be made of the member of stacked polaroid and the optical layers more than 2 layers or 3 layers.Therefore, also can be the reflection-type ellipsoidal polarizing plate that forms of combination above-mentioned reflection type polarizer or semi-transmission type polaroid and polarizer or semi-transmission type ellipsoidal polarizing plate etc.
The stacked optics of above-mentioned optical layers on polaroid, can utilize that independent successively stacked mode forms in the manufacturing processed of liquid crystal indicator etc., but good through being laminated in advance at aspects such as quality of stability or assembly operations to the member of optics, therefore have the advantage of the manufacturing process that can improve liquid crystal indicator etc.In stacked, can use suitable adhesion means such as bonding coat.When bonding above-mentioned polaroid and other optical layers, their optic axis can adopt the arrangement angles that suits according to target phase difference characteristic etc.
Also have, on each layers such as the optics of adhesion type optics of the present invention, binder layer, can utilize and for example use mode that bigcatkin willow acid esters compound or benzo phenol (benzophenol) compounds, benzotriazole compound or UV light absorber such as cyanoacrylate compound, nickel coordination compound compounds handle etc., make it to have ultraviolet absorption ability etc.
Adhesion type optics of the present invention is preferred for the formation of various image display devices such as liquid crystal indicator etc.Liquid crystal indicator can form according to method in the past.Promptly, in general, liquid crystal indicator can pass through combination of liquid crystals unit and adhesion type optics aptly, and the component parts such as the lighting system that adds as required and the driving circuit of packing into etc. and form, in the present invention, except using optics of the present invention, be not particularly limited, can form according to method in the past.For liquid crystal cells, also can use for example liquid crystal cells of any type such as TN type or STN type, π type.
Can be formed on liquid crystal cells one-sided or double sided arrangements the liquid crystal indicator of adhesion type optics, in lighting system, used the suitable liquid crystal indicator such as device of backlight or reflector.At this moment, optics of the present invention can be arranged on the one-sided or bilateral of liquid crystal cells.When optics was arranged on bilateral, they both can be identical materials, also can be different materials.In addition, when forming liquid crystal indicator, can be on suitable position suitable parts such as for example diffuser plate of configuration more than 1 layer or 2 layers, antiglare layer, antireflection film, protecting sheet, prism array, lens arra thin slice, light diffusing sheet, backlight.
Then, Organnic electroluminescent device (organic EL display) is described.In general, on transparency carrier, stack gradually transparency electrode, organic luminous layer and metal electrode in the organic El device and form twinkler (organic electroluminescent body).Here, organic luminous layer is the duplexer of various organic films, and known have: for example duplexer of the duplexer of hole injection layer that is made of triphenylamine derivative etc. and the luminescent layer that is made of epipolic organic solids such as anthracenes or this kind luminescent layer and the electron injecting layer that is made of perylene derivative etc. or the various combinations such as duplexer of these hole injection layers, luminescent layer and electron injecting layer.
Organic EL display carries out luminous according to following principle, promptly, by on transparency electrode and metal electrode, adding voltage, injected hole and electronics in organic luminous layer, the energy excitation fluorescent substance that produces by the compound of these holes and electronics, when the fluorescent substance that is excited is got back to ground state, will radiate bright dipping.Recombination mechanism wherein is identical with general diode, also can infer thus, and electric current and luminous intensity demonstrate with respect to impressed voltage and follow the stronger non-linear of rectification.
In organic EL display, in order to take out the light that produces in the organic luminous layer, at least one side's electrode must be transparent, will be used as anode by the transparency electrode that tin indium oxide transparent conductive bodies such as (ITO) is made usually.On the other hand, thereby improve luminous efficiency easily as if the injection that will make electronics, it is crucial using the less material of work function on negative electrode, uses metal electrodes such as Mg-Ag, Al-Li usually.
In having the organic EL display of this formation, organic luminous layer is that film as thin as a wafer about 10nm constitutes by thickness.Therefore, organic luminous layer is also the same with transparency electrode, and light is fully seen through basically.Its result, when not luminous from the surperficial incident of transparency carrier and see through transparency electrode and organic luminous layer and can be once more penetrating to the face side of transparency carrier at the light of metal electrode reflection, therefore, when carrying out identification from the outside, the display surface of organic El device is as minute surface.
In the organic EL display that comprises organic electroluminescent body as described below, can polaroid be set in the face side of transparency electrode, simultaneously between these transparency electrodes and polaroid, polarizer is set, in the above-mentioned organic electroluminescent body, be provided with transparency electrode by applying the face side that voltage carries out luminous organic luminous layer, the rear side at organic luminous layer is provided with metal electrode simultaneously.
Become the effect of polarized light because polarizer and polaroid have to make from outside incident and at the light of metal electrode reflection, so, have the feasible effect that can't pick out the minute surface of metal electrode from the outside by this polarized light effect.Particularly, adopt 1/4 wavelength plate to constitute polarizer and the angle of the polarization direction of polaroid and polarizer is adjusted into π/4 o'clock, can cover the minute surface of metal electrode fully.
That is, the exterior light that incides this organic EL display has only the rectilinearly polarized light composition because of the existence of polaroid and sees through.This rectilinearly polarized light generally can be converted to elliptically polarized light by polarizer, and when polarizer be the angle of the polarization direction of 1/4 wavelength plate and polaroid and polarizer when being π/4, will become circularly polarized light.
This circularly polarized light sees through transparency carrier, transparency electrode, organic film, reflects on metal electrode, sees through organic film, transparency electrode, transparency carrier afterwards once more, converts rectilinearly polarized light once more to by polarizer.Because therefore the polarization direction quadrature of this rectilinearly polarized light and polaroid can't see through polaroid.Its result can be covered the minute surface of metal electrode fully.
In order to protect adhesive face, the barrier sheet (perhaps release liner, stripping film etc.) of can on adhesive surface, fitting in the adhesion type optics of the present invention in case of necessity.Base material as constituting barrier sheet has paper or plastics film, but from the outstanding viewpoint of surface smoothness, preferably uses plastics film.
As this plastics film; so long as can protect the film of above-mentioned binder layer; just be not particularly limited; can be exemplified as polyethylene; polypropylene; poly-1-butylene; poly--4-methyl-1-pentene; the polyhutadiene film; poly-methyl pentene film; ethylene-propylene copolymer; ethene-butene-1 copolymer; ethylene-vinyl acetate copolymer; ethylene-ethyl acrylate copolymer; polyolefin films such as ethylene-vinyl alcohol copolymer; polyethylene terephthalate; PEN; polyester films such as polybutylene terephthalate; the polyacrylic acid ester film; polyurethane film; polystyrene film; nylon 6; nylon 6; 6; polyamide layers such as partially aromatic polyamide; polyvinyl chloride film; the vinyl chloride copolymer film; the polyvinylidene chloride film, polycarbonate film etc.
The thickness of above-mentioned film is generally 5～200 μ m, about preferred 10～100 μ m.Can be on the binder layer binding face of above-mentioned film, utilize the releasing agent, silicon dioxide powder etc. of silicone, fluorine class, chain alkyl class or fatty acyl amide and suitably implement releasing agent and handle.
Adhesion type optics of the present invention is preferred for making various display unit such as liquid crystal indicator or touch panel.Forming on the polaroid or optical materials such as polarizer, brightness improving plate or antiglare sheet of optics, also can use UV light absorber etc. and make it to have ultraviolet absorption ability.As UV light absorber, can be exemplified as salicylate compounds or benzophenone compound, benzotriazole compound, cyanoacrylate compound, nickel complex salt compounds etc.
Embodiment
Below, embodiment of concrete expression formation of the present invention and effect etc. is described.Wherein, the assessment item among the embodiment etc. is to measure according to method as follows.
The measurement of＜acid number 〉
Acid number is to use automatic titration device, and (flat natural pond industry system COM-550) is measured, and obtains according to following formula.
A＝{(Y-X)×f×5.611}/M
A: acid number
Y: the titer of sample solution (ml)
X: only to the titer (ml) of the solution of mixed solvent 50g
F: the factor of volumetric soiutions (factor)
M: the weight of polymer samples (g)
Measuring condition is as follows.
Sample solution: the about 0.5g of polymer samples is dissolved among mixed solvent (toluene/2-propyl alcohol/distilled water=50/49.5/0.5, the weight ratio) 50g and makes sample solution.
Volumetric soiutions: 0.1N, 2-propyl alcohol potassium hydroxide solution (pure pharmaceutical worker already makes with light, is used for the test of petroleum products neutralization value)
Electrode: glass electrode, GE-101, relatively electrode, RE-201
Measurement pattern: petroleum products neutralization value test 1
The measurement of＜molecular weight 〉
Molecular weight is to use GPC device (eastern ソ one system, HLC-8220GPC) and measures.Measuring condition is as follows.
Sample concentration: 0.2wt% (THF solution)
Sample injection rate: 10 μ l
Eluant: THF
Flow velocity: 0.6ml/min
Measuring speed: 40 ℃
Post:
Sample column:
TSK guard column (guardcolumn) Super HZ-H (1)+tsk gel Super HZM-H (2)
Reference column:
Tsk gel Super H-RC (1)
Detector: differential refractometer (RI)
Also have, molecular weight is obtained as the polystyrene conversion value.
The measurement of＜second-order transition temperature Tg 〉
Measure second-order transition temperature Tg (℃) time, as the second-order transition temperature Tgn of the homopolymer that forms by each monomer (℃) and use following literature value, and obtain by following formula.
Formula:
1/(Tg+273)＝∑[Wn/(Tgn+273)]
[in the formula, Tg (℃) expression multipolymer second-order transition temperature.Wn (-) represents each monomeric weight fraction, Tgn (℃) second-order transition temperature of the homopolymer that forms by each monomer of expression, n represents each monomeric kind.]
Literature value:
Vinylformic acid ester in the different ninth of the ten Heavenly Stems :-82 ℃
2-EHA :-70 ℃
Butyl acrylate :-55 ℃
Vinylformic acid 2-hydroxyethyl ester :-15 ℃
Diethyl acrylamide: 81 ℃
Vinylformic acid: 106 ℃
Wherein, literature value is with reference to the record in " synthesizing, design and new purposes exploitation of acrylic resin " (middle part is managed development centre publishing department and issued).
The evaluation of＜toluene solubility 〉
Add the toluene (pure pharmaceutical worker already makes with light, superfine) of 9 weight parts in the ionic liquid of 1 weight part, normal temperature (25 ℃) mixes stirring 10 minutes down, leaves standstill then 30 minutes.
Then, its solvability is estimated, judged the toluene solubility for visual time.Wherein, metewand is that the state that will not have isolate and uniform dissolution is judged as " solvable " (having the toluene solubility).
＜ionic liquid structural analysis 〉
The structural analysis of ionic liquid is measured and is carried out by NMR measurement, XRF measurement, FT-IR.
[NMR measurement]
The NMR measurement is to use nuclear magnetic resonance device, and (NEC system EX-400) is carried out under following measuring condition.
Observed frequency: 400MHz ( 1H), 100MHz ( 13C)
Measure solvent: acetone-d6
Measure temperature: 23 ℃
[XRF measurement]
The XRF measurement is to use the sweep type fluorescent x-ray analyzer, and (motor system of science ZSX-100e) is carried out under following measuring condition.
Measuring method: filter paper method
X-ray source: Rh
[FT-IR measurement]
The FT-IR measurement is to use infrared spectrophotometer, and (the Nicolet system Magna-560) is carried out under following measuring condition.
Measuring method: ATR method
Detector: DTGS
Resolving power: 4.0cm -1
Cumulative number: 64 times
Below, example I～V is described.
[example I]
Production Example I-1
(acrylic polymers A)
In stream of nitrogen gas, under 65 ℃, make 2-EHA 200g, vinylformic acid 2-hydroxyethyl ester 8g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 312g 6 hours, the solution (40 weight %) that obtain Tg=-68 ℃, weight-average molecular weight and be 500,000, acid number is 0 acrylic polymers.
Production Example I-2
(acrylic polymers B)
In stream of nitrogen gas, under 65 ℃, make n-butyl acrylate 200g, vinylformic acid 2-hydroxyethyl ester 8g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 625g 6 hours, the solution (25 weight %) that obtain Tg=-54 ℃, weight-average molecular weight and be 540,000, acid number is 0 acrylic polymers.
Production Example I-3
(acrylic polymers C)
In stream of nitrogen gas, under 65 ℃, make 2-EHA 200g, acrylate 8g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 312g 6 hours, the solution (40 weight %) that obtain Tg=-66 ℃, weight-average molecular weight and be 540,000, acid number is 30 acrylic polymers.
Production Example I-4
(acrylic polymers D)
In stream of nitrogen gas with high voltage mercury lamp to 2-EHA 200g, 1-hydroxycyclohexylphenylketone (Chiba Specialty chemicals system, Irgacure 184) 0.1g, benzyl dimethyl ketal (Chiba Specialty chemicals system, Irgacure 651) the mixture irradiation ultraviolet radiation of 0.1g, obtain percent polymerization and be 10% partial polymer (weight-average molecular weight is 2,200,000, acid number be 0).
Production Example I-5
(antistatic agent A)
With the mixture of vinyl acetic monomer 10g dilution lithium perchlorate (236 ℃ of fusing points) 0.2g, polypropylene glycol (diol type, number-average molecular weight 2,000) 9.8g, make antistatic agent solution (50 weight %).
Production Example I-6
(antistatic agent B)
With lauryl trimethyl ammonium muriate (Tokyo change into industry system, 25 ℃ down for solid-state) 10 weight parts of vinyl acetic monomer 20 weight parts and Virahol 20 weight parts dilution, make antistatic agent solution (20 weight %) as the cationic tensio-active agent.
Example I-1
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example I-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-butyl-3-picoline trifluoro-methanyl sulfonate (the 25 ℃ liquid down) 0.1g as ionic liquid, isocyanuric acid ester body (the Japanese polyurethane industry system of hexamethylene diisocyanate, Coronate HX) 0.8g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.
(making of adhesive sheet)
Aforesaid propylene acid binder solution is coated on the single face of pet film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃.Then, the one side of fitting on the surface of above-mentioned binder layer has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated, makes adhesive sheet.
Example I-2
(modulation of binder composition)
2.0g similarly modulates acryloid cement solution as outside the ionic liquid with example I-1 with two (trifluoromethane sulfonyl group) imines of diallyl dimethyl ammonium (25 ℃ liquid down).
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example I-1 is similarly made adhesive sheet.
Example I-3
(modulation of binder composition)
The solution (25 weight %) of the acrylic polymers B that will obtain in Production Example I-2 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-butyl-3-picoline trifluoro-methanyl sulfonate (25 ℃ liquid down) 0.1g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system as ionic liquid, trade(brand)name Coronate L) 1.1g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.6g of crosslinking catalyst, modulation acryloid cement solution.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example I-1 is similarly made adhesive sheet.
Example I-4
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers C that will obtain in Production Example I-3 with vinyl acetic monomer is diluted to 20 weight %; in this solution 100g, add as two (trifluoromethane sulfonyl group) imines of the diallyl dimethyl ammonium of ionic liquid (25 ℃ liquid down) 2.0g; 1; two (the N of 3-; N-diglycidyl amino methyl) hexanaphthene (Mitsubishi's gas chemistry system; trade(brand)name TETRAD-C) 0.7g; TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system; trade(brand)name Coronate L) 0.3g, modulation acryloid cement solution.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example I-1 is similarly made adhesive sheet.
Example I-5
(modulation of binder composition)
Add 1-butyl-3-picoline trifluoro-methanyl sulfonate (25 ℃ liquid down) 0.2g, Viscoat 295 1.5g, benzyl dimethyl ketal (Chiba Specialty chemicals system among the partial polymer 100g that in Production Example I-4, obtains as ionic liquid, Irgacure651) 0.1g, modulation acryloid cement solution.
(making of adhesive sheet)
Aforesaid propylene acid binder solution is coated on the single face of pet film, and making its thickness is 20 μ m, and then covers the pet film through silicone-treated of thick 25 μ m in the above.With high voltage mercury lamp with illumination 37mW/cm 2, light quantity 660mJ/cm 2Condition this sheet is carried out uviolizing, make adhesive sheet.
Example I-6
(modulation of binder composition)
0.1g similarly modulates acryloid cement solution as outside the ionic liquid with example I-1 with two (trifluoromethane sulfonyl group) imines of 1-butyl-3-picoline (25 ℃ liquid down).
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example I-1 is similarly made adhesive sheet.
Comparative Example I-1
Except not adding the ionic liquid, and example I-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the surface protective film of thick 20 μ m.
Comparative Example I-2
Except not adding the ionic liquid, and example I-3 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the surface protective film of thick 20 μ m.
Comparative Example I-3
Except not adding the ionic liquid, and example I-4 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the surface protective film of thick 20 μ m.
Comparative Example I-4
Except not adding the ionic liquid, and example I-5 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the surface protective film of thick 20 μ m.
Comparative Example I-5
For example I-1, except antistatic agent A solution (the 50 weight %) 4.0g that uses Production Example I-5 replaces the ionic liquid, and example I-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made adhesive sheet.
Comparative Example I-6
For example I-1, except antistatic agent B solution (the 20 weight %) 10g that uses Production Example I-6 replaces the ionic liquid, and example I-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the adhesive sheet of thick 20 μ m.
Reference example I-1
8.0g is as the ionic liquid, and example I-1 is similarly modulated acryloid cement solution except adding 1-butyl-3-picoline trifluoro-methanyl sulfonate (25 ℃ liquid down).Except using this acryloid cement solution as acryloid cement solution, and example I-1 is similarly made the surface protective film of thick 20 μ m.
About the adhesive sheet that in the above embodiments, comparative example and reference example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.
＜peel off the measurement of static voltage 〉
Adhesive sheet is cut into the size of wide 70mm, long 100mm, as shown in Figure 1, is arranged on the sample stationary platen.An end of barrier sheet is fixed on the sutomatic winding machine, peels off with the condition of 150 ° of peel angle, peeling rate 10m/min.Use is fixed on electric potential measuring instrument on the prescribed position, and (springtime motor system KSD-0103) is measured the current potential of adhesive surface.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
The evaluation of＜contaminative 〉
The cellulose triacetate film (Fujiphoto system, Off ジ タ Star Network) of thick 80 μ m is cut into wide 70mm, long 100mm, after in 60 ℃ aqueous sodium hydroxide solutions (10 weight %), flooding 1 minute, cleans and the making adherend with distilled water.Under the environment of 23 ℃ * 50%RH, place after the above-mentioned adherend 1 day, fit to be cut into the adhesive sheet and the adherend of wide 70mm, long 100mm size and to have made with hand and sneak into bubble between them, thus the making assess sample.After under 50 ℃ environment, placing 1 day, under the environment of 23 ℃ * 50%RH, placed 2 hours, subsequently with hand release adhesive sheet from the adherend, the pollutional condition on the visual adherend of observation down surface.Metewand is, is zero in the time of can not confirming to pollute, in the time of can confirming to pollute be *.
＜bonding force measurement 〉
The cellulose triacetate film (Fujiphoto system, Off ジ タ Star Network) of thick 80 μ m is cut into wide 70mm, long 100mm, after in 60 ℃ aqueous sodium hydroxide solutions (10 weight %), flooding 1 minute, cleans and the making adherend with distilled water.Under the environment of 23 ℃ * 50%RH, place after the above-mentioned adherend 1 day, use as the adherend that is used to estimate bounding force.The adhesive sheet that will be cut into the size of wide 25mm, long 80mm with the pressure of 0.25MPa is layered in above-mentioned evaluation with on the adherend, makes assess sample.Placed 30 minutes in stacked back, afterwards, the bounding force when using omnipotent tensile test machine to measure to peel off with the condition of 180 ° of peeling rate 30m/ minutes, peel angle.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
Above-mentioned result is as shown in table 1.
Table 1
Peel off static voltage [kV] Contaminative Bounding force [N/25mm]
Example I-1 0.0 ○ 1.1
Example I-2 0.0 ○ 2.5
Example I-3 0.0 ○ 6.4
Example I-4 0.5 ○ 1.2
Example I-5 0.0 ○ 1.7
Example I-6 0.0 ○ 1.1
Comparative Example I-1 1.9 ○ 1.5
Comparative Example I-2 0.7 ○ 6.5
Comparative Example I-3 1.2 ○ 1.1
Comparative Example I-4 2.0 ○ 1.8
Comparative Example I-5 0.0 × 1.6
Comparative Example I-6 0.0 × 0.3
Reference example I-1 0.0 × 0.3
By the result of above-mentioned table 1 as can be known, the adhesive sheet of embodiments of the invention I-1～6 is compared with the adhesive sheet that does not contain ionic liquid in the Comparative Example I-1～4, can suppress to peel off static voltage when keeping bounding force substantially.In addition, the adhesive sheet of embodiments of the invention I-1～6 is compared with Comparative Example I-5～6, does not have contaminative.As can be known, the binder composition of example I-1～6 is static electricity resistance and the outstanding binder composition of low contaminative.
Particularly, in Comparative Example I-6,, caused the decline of bounding force so occur oozing out, in addition, in Comparative Example I-5, utilized the anti-effect of oozing out of ligand compound materialization of an alkali metal salt abundant inadequately because used tensio-active agent with chain alkyl.
[example II]
Production Example II-1
As the acrylic polymers A that makes II-1, use the solution (40 weight %) of acrylic polymers of the acrylic polymers A (Tg=-68 ℃, weight-average molecular weight are 500,000, acid number be 0) of the Production Example I-1 in the example I.
Production Example II-2
(acrylic polymers B)
In stream of nitrogen gas, under 65 ℃, make vinylformic acid ester 200g in the different ninth of the ten Heavenly Stems, vinylformic acid 2-hydroxyethyl ester 8g, 2,2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 312g reaction 6 hours, the solution (40 weight %) that obtain Tg=-80 ℃, weight-average molecular weight and be 540,000, acid number is 0 acrylic polymers.
Production Example II-3
(acrylic polymers C)
In stream of nitrogen gas with high voltage mercury lamp to 2-EHA 200g, 1-hydroxycyclohexylphenylketone (Chiba Specialty chemicals system, Irgacure 184) 0.1g, benzyl dimethyl ketal (Chiba Specialty chemicals system, Irgacure 651) the mixture irradiation ultraviolet radiation of 0.1g, obtain percent polymerization and be 10% partial polymer (weight-average molecular weight is 2,200,000, acid number be 0).
Production Example II-4
(acrylic polymers D)
In stream of nitrogen gas, under 65 ℃, make 2-EHA 200g, vinylformic acid 0.4g, vinylformic acid 2-hydroxyethyl ester 3.6g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 312g 6 hours, the solution (40 weight %) that obtain Tg=-66 ℃, weight-average molecular weight and be 560,000, acid number is 1.3 acrylic polymers.
Production Example II-5
(acrylic polymers E)
In stream of nitrogen gas, under 65 ℃, make 2-EHA 200g, vinylformic acid 8g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 312g 6 hours, the solution (40 weight %) that obtain Tg=-66 ℃, weight-average molecular weight and be 540,000, acid number is 30 acrylic polymers.
Production Example II-6
(antistatic agent A)
As the antistatic agent A of Production Example II-6, use the antistatic agent solution (50 weight %) of the antistatic agent A of the Production Example I-5 in the example I.
Production Example II-7
(anti-electrostatic processing film)
The mixed solvent that use is made of water 30 weight parts and methyl alcohol 70 weight parts, dilution antistatic agent (ソ Le ベ Star Network ス system, little solver RMd-142 is a principal constituent with stannic oxide and vibrin) 10 weight parts are modulated antistatic agent solution thus.
Use wire bar to go up the antistatic agent solution that coating obtains at polyethylene terephthalate (PET) film (thick 38 μ m), desolvate by removing in dry 1 minute down at 130 ℃, thereby form antistatic backing (thick 0.2 μ m), and make anti-electrostatic thus and handle film.
Production Example II-8
(antistatic agent B)
As the antistatic agent B of Production Example II-8, use the antistatic agent solution (20 weight %) of the antistatic agent B of the Production Example I-6 in the example I.
Example II-1
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example II-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-butyl-3-picoline trifluoro-methanyl sulfonate (Japanese カ one リ Star ト system as ionic liquid, BMP-Trf, liquid state under 25 ℃) the isocyanuric acid ester body of 0.1g, hexamethylene diisocyanate (Japanese polyurethane industry system, Coronate HX) 0.8g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.
(making of adhesive sheet)
Aforesaid propylene acid binder solution is coated in the anti-electrostatic that obtains among the Production Example II-7 handles on the face opposite of film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃ with the anti-electrostatic treated side.Then, the one side of fitting on the surface of above-mentioned binder layer has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated, makes adhesive sheet.
Example II-2
(modulation of binder composition)
With N; two (trifluoromethane sulfonyl group) imines of N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium (Northeast chemistry system; liquid state under 25 ℃) (the vinyl acetic monomer solution of 10 weight %) 0.5g similarly modulates acryloid cement solution as outside the ionic liquid with example II-1.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Example II-3
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers B that will obtain in Production Example II-2 with vinyl acetic monomer is diluted to 20 weight %, and except using this solution 100g, and example II-1 is similarly modulated acryloid cement solution.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Example II-4
(modulation of binder composition)
Add 1-butyl-3-picoline trifluoro-methanyl sulfonate (Japanese カ one リ Star ト system among the partial polymer 100g that in Production Example II-3, obtains as ionic liquid, BMP-Trf, liquid state under 25 ℃) 0.2g, Viscoat 295 1.5g, benzyl dimethyl ketal (ChIIbaSpecIIalty chemIIcals system, IIrgacure 651) 0.1g, modulation acryloid cement solution.
(making of adhesive sheet)
Aforesaid propylene acid binder solution is coated in the anti-electrostatic that obtains among the Production Example II-7 to be handled on the one side opposite with the anti-electrostatic treated side of film, making its thickness is 20 μ m, and then covers the pet film through silicone-treated of thick 25 μ m in the above.With high voltage mercury lamp with illumination 37mW/cm 2, light quantity 660mJ/cm 2Condition this sheet is carried out uviolizing, make adhesive sheet.
Example II-5
(modulation of binder composition)
Except (the vinyl acetic monomer solution of 10 weight %) 0.5g is as outside the ionic liquid, and example II-1 is similarly modulated acryloid cement solution with 1-hexyl-3-Methylimidazole trifluoro-methanyl sulfonate (ACROSORGANICS system, 25 ℃ liquid down).
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Example II-6
(modulation of binder composition)
Except two (trifluoromethane sulfonyl group) imines of 1-butyl-3-picoline (25 ℃ liquid down for Japanese カ one リ Star ト system, BMP-IL) 0.1g is similarly modulated acryloid cement solution as outside the ionic liquid with example II-1.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Example II-7
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example II-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-ethyl-3-Methylimidazole (trifluoromethane sulphonyl) trifluoroacetamide (ト Network ヤ マ system as ionic liquid, trade(brand)name: EMI-TSAC, 25 ℃ are liquid down) 0.08g, the isocyanuric acid ester body of hexamethylene diisocyanate (Japanese polyurethane industry system, Coronate HX) 0.4g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Example II-8
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example II-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add fatty acyl amide ionic liquid (wide flourish chemical industry system as ionic liquid, IL-A1, liquid state under 25 ℃) the isocyanuric acid ester body of 0.1g, hexamethylene diisocyanate (Japanese polyurethane industry system, Coronate HX) 0.5g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.
(making of adhesive sheet)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and example II-1 is similarly made adhesive sheet.
Comparative Example I I-1
Except not adding the ionic liquid, and example II-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-2
The acryloid cement solution of making among the Comparative Example I I-1 is coated on the single face of pet film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃.Then, the one side of fitting on the surface of above-mentioned binder layer has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated, makes adhesive sheet.
Comparative Example I I-3
Except not adding the ionic liquid, and example II-3 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-4
Except not adding the ionic liquid, and example II-4 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-5
The solution (40 weight %) of the acrylic polymers D that will obtain in Production Example II-4 with vinyl acetic monomer is diluted to 20 weight %, and except using this solution 100g, and example II-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-6
The solution (40 weight %) of the acrylic polymers E that will obtain in Production Example II-5 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-butyl-3-picoline trifluoro-methanyl sulfonate (Japanese カ one リ Star ト system, BMP-Trf, 25 ℃ are liquid down) 0.2g, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene (Mitsubishi's gas chemistry system, trade(brand)name TETRAD-C) 0.7g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system, trade(brand)name Coronate L) 0.3g, modulation acryloid cement solution.Except using this acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-7
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example II-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add antistatic agent solution (50 weight %) 4.0g, the TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system of Production Example II-6, trade(brand)name Coronate L) 0.53g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-8
For example II-1, except antistatic agent B solution (the 20 weight %) 0.5g that uses Production Example II-8 replaces the ionic liquid, and example II-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
Comparative Example I I-9
The acryloid cement solution that to make in example II-2 is coated on the single face of pet film, heats 3 minutes down at 110 ℃, forms the binder layer of thick 20 μ m.Then, the one side of fitting on the surface of above-mentioned binder layer has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated, makes adhesive sheet.
Reference example II-1
Butyl-3-picoline trifluoro-methanyl sulfonate 8.0g is as the ionic liquid, and example II-1 is similarly modulated acryloid cement solution except adding 1-.Except using this acryloid cement solution as acryloid cement solution, and example II-1 is similarly made the adhesive sheet of thick 20 μ m.
About the adhesive sheet that in the above embodiments, comparative example and reference example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.
＜peel off the measurement of static voltage 〉
Adhesive sheet is cut into the size of wide 70mm, long 130mm, after peeling off barrier sheet, so that exposing the mode of 30mm, the end of one side is crimped on polaroid (day eastern electrician's system with pulling cylinder, SEG1425EWVAGS2B, size: wide 70mm, long 100mm) on the surface, wherein, described polaroid is fitted in and has eliminated on the acrylic panel of the thick 1mm of electrostatic, wide 70mm, long 100mm in advance.After under the environment of 23 ℃ * 50%RH, placing 1 day, as shown in Figure 2, sample is arranged on the prescribed position.The end that to expose the side of 30mm is fixed on the sutomatic winding machine, peels off with the condition of 150 ° of peel angle, peeling rate 10m/min.(springtime motor system KSD-0103) is measured the current potential on the polaroid surface that produces this moment with being fixed on electric potential measuring instrument on the prescribed position.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
The evaluation of＜contaminative 〉
Measure above-mentioned peel off static voltage after, with hand fit once more the adhesive sheet of being stripped from and measure after polaroid, and make and sneak into bubble between them, thereby make assess sample.After under the environment of 23 ℃ * 50%RH, placing 1 month, with hand release adhesive sheet from the adherend, the visual pollutional condition of observing the adherend surface down.Metewand is, is zero in the time of can not confirming to pollute, in the time of can confirming to pollute be *.
＜bonding force measurement 〉
The bounding force measuring method of example II is identical with the situation of the foregoing description I.
Above-mentioned result is as shown in table 2.
Table 2
Peel off static voltage [kV] Contaminative Bounding force [N/25mm]
Example II-1 0.0 ○ 1.1
Example II-2 -0.3 ○ 1.3
Example II-3 0.0 ○ 1.2
Example II-4 0.0 ○ 1.7
Example II-5 0.0 ○ 1.5
Example II-6 0.0 ○ 1.1
Example II-7 0.0 ○ 2.2
Example II-8 0.0 ○ 2.3
Comparative Example I I-1 -1.1 ○ 1.5
Comparative Example I I-2 -0.8 ○ 1.4
Comparative Example I I-3 -1.4 ○ 1.7
Comparative Example I I-4 -1.2 ○ 1.8
Comparative Example I I-5 -0.7 ○ 1.3
Comparative Example I I-6 -0.9 ○ 0.9
Comparative Example I I-7 0.0 × 2.1
Comparative Example I I-8 0.0 × 0.4
Comparative Example I I-9 -1.0 ○ 1.3
Reference example II-1 0.0 × 0.3
By the result of above-mentioned table 2 as can be known, the adhesive sheet of embodiments of the invention II-1～8 is compared with the adhesive sheet that does not contain ionic liquid in Comparative Example I I-1～4, can suppress to peel off static voltage when keeping bounding force substantially.In addition, the adhesive sheet of embodiments of the invention II-1～8 is compared with Comparative Example I I-7～9, does not have contaminative.Therefore, the binder composition of example II-1～8 is static electricity resistance and the outstanding binder composition of low contaminative as can be known.
Particularly, in Comparative Example I I-8,,, in addition, in Comparative Example I I-7, utilize the anti-effect of oozing out of ligand compound materialization of an alkali metal salt abundant inadequately so occurred oozing out because used tensio-active agent.
[EXAMPLE III]
Production Example III-1
(acrylic polymers A)
As the acrylic polymers A of Production Example III-1, use the solution (40 weight %) of acrylic polymers of the acrylic polymers A (Tg=-68 ℃, weight-average molecular weight are 500,000, acid number be 0) of the Production Example I-1 in the example I.
Production Example III-2
(acrylic polymers B)
As the acrylic polymers A of Production Example III-2, use the solution (25 weight %) of acrylic polymers of the acrylic polymers B (Tg=-54 ℃, weight-average molecular weight are 540,000, acid number be 0) of the Production Example I-2 in the example I.
Production Example III-3
(acrylic polymers C)
In stream of nitrogen gas, under 65 ℃, make 2-EHA 156g, diethyl acrylamide 40g, vinylformic acid 4g, 2, the mixture reaction of 2 '-Diisopropyl azodicarboxylate 0.4g, vinyl acetic monomer 300g 6 hours, the solution (40 weight %) that obtain Tg=-49 ℃, weight-average molecular weight and be 560,000, acid number is 15 acrylic polymers.
Production Example III-4
(polaroid)
Make the PVA (PVOH) FILM swelling 1 minute of the polymerization degree 1700, thick 80 μ m with 30 ℃ warm water baths, in being the aqueous solution (30 ℃) of 0.3 weight %, the iodine concentration of being made of iodine and potassiumiodide (weight ratio=1: 10) is stretched to about 3 times then, in 50 ℃ 4 weight % boric acid aqueous solutions, stretch subsequently, make its total stretching ratio reach 6 times.Then, dipping obtains polariscope 40 ℃ of following dryings 5 minutes after 5 seconds in 30 ℃ 4 weight % potassium iodide aqueous solutions.The tackiness agent that use is made of the polyvinyl alcohol water solution of 7 weight %, this polariscopic two-sided the cellulose triacetate film of handling through saponification of stacked thick 80 μ m, make polaroid.Saponification is handled to flood in 60 ℃ aqueous sodium hydroxide solution (10 weight %) and was carried out in 1 minute.
EXAMPLE III-1
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example III-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add glycidyl trimethyl ammonium trifluoro-methanyl sulfonate (25 ℃ liquid down) 2.0g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system as ionic liquid, trade(brand)name Coronate L) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Aforesaid propylene acid binder solution is coated on the silicone-treated face of pet film of the thick 38 μ m that implement silicone-treated,, forms the binder layer of thick 25 μ m 110 ℃ of heating 3 minutes down.Then, the polaroid that will make in Production Example III-4 and above-mentioned tackiness agent aspect are fitted, and make the adhesion type optics.
EXAMPLE III-2
(modulation of binder composition)
The solution (25 weight %) of the acrylic polymers B that will obtain in Production Example III-2 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add 1-butyl-3-picoline trifluoro-methanyl sulfonate (25 ℃ liquid down) 0.2g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system as ionic liquid, trade(brand)name Coronate L) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
EXAMPLE III-3
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers that will obtain in Production Example III-3 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add diallyl dimethyl ammonium trifluoro-methanyl sulfonate (25 ℃ liquid down) 2.0g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system as ionic liquid, trade(brand)name Coronate L) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
EXAMPLE III-4
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example III-1 with vinyl acetic monomer is diluted to 20 weight %; in this solution 100g, add as two (trifluoromethane sulfonyl group) imines of the glycidyl trimethyl ammonium of ionic liquid (25 ℃ liquid down) 2.0g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system; trade(brand)name Coronate L) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Aforesaid propylene acid binder solution is coated on the silicone-treated face of pet film of the thick 38 μ m that implement silicone-treated,, forms the binder layer of thick 25 μ m 110 ℃ of heating 3 minutes down.Then, the polaroid that will make in Production Example III-4 and above-mentioned tackiness agent aspect are fitted, and make the adhesion type optics.
EXAMPLE III-5
(modulation of binder composition)
The solution (25 weight %) of the acrylic polymers B that will obtain in Production Example III-2 with vinyl acetic monomer is diluted to 20 weight %; in this solution 100g, add as two (trifluoromethane sulfonyl group) imines of the 1-butyl-3-picoline of ionic liquid (25 ℃ liquid down) 0.2g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system; trade(brand)name Coronate L) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
EXAMPLE III-6
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers that will obtain in Production Example III-3 with vinyl acetic monomer is diluted to 20 weight %; in this solution 100g, add as two (trifluoromethane sulfonyl group) imines of the diallyl dimethyl ammonium of ionic liquid (25 ℃ liquid down) 2.0g, TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system; trade(brand)name CoronateL) 0.13g, modulation acryloid cement solution.
(making of adhesion type optics)
Except using as acryloid cement solution in above-mentioned the synthetic acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
Comparative Example I II-1
Except not using the ionic liquid, and EXAMPLE III-1 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
Comparative Example I II-2
Except not using the ionic liquid, and EXAMPLE III-2 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
Comparative Example I II-3
Except not using the ionic liquid, and EXAMPLE III-3 is similarly modulated acryloid cement solution.Except using this acryloid cement solution as acryloid cement solution, and EXAMPLE III-1 is similarly made the adhesion type optics.
About the adhesive sheet that in the above embodiments, comparative example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.
Production Example III-5
(anti-electrostatic is handled the making of pet film)
The anti-electrostatic of Production Example II-7 in the example II is handled film handle pet film as the anti-electrostatic of Production Example III-5.
Production Example III-6
(modulation of binder composition)
The solution (40 weight %) of the acrylic polymers A that will obtain in Production Example III-1 with vinyl acetic monomer is diluted to 20 weight %, in this solution 100g, add isocyanuric acid ester body (the Japanese polyurethane industry system of hexamethylene diisocyanate, Coronate HX) 0.8g, as dibutyl tin laurate (the vinyl acetic monomer solution of the 1 weight %) 0.4g of crosslinking catalyst, modulation acryloid cement solution.
Production Example III-7
(making of protective film)
Aforesaid propylene acid binder solution is coated in the anti-electrostatic that obtains among the Production Example III-5 handles on the face opposite of pet film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃ with the anti-electrostatic treated side.Then, the one side of fitting on the surface of above-mentioned binder layer has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated, makes protective film.
＜peel off the measurement of static voltage 〉
After the barrier sheet of peeling off the adhesion type optics that is cut into wide 70mm, long 100mm size, be fitted in and eliminated on the acrylic panel of the thick 1mm of electrostatic, wide 70mm, long 100mm in advance with pulling cylinder, the making adherend.The protective film that obtains among the Production Example III-7 is cut into the size of wide 70mm, long 130mm; after peeling off barrier sheet, so that the mode that 30mm is exposed in the end of one side is crimped on and has eliminated on the polaroid surface of the above-mentioned adherend of electrostatic in advance with pulling cylinder.After under the environment of 23 ℃ * 50%RH, placing 1 day, as follows, sample is contained on the prescribed position.The end that to expose the side of 30mm is fixed on the sutomatic winding machine, peels off with the condition of 150 ° of peel angle, peeling rate 10m/min.(springtime motor system KSD-0103) is measured the current potential on the polaroid surface that produces this moment with being fixed on electric potential measuring instrument on the prescribed position.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
＜bonding force measurement 〉
After the barrier sheet of peeling off the adhesion type optics that is cut into wide 25mm, long 100mm, use the shell of compression of 0.25MPa to be stacked on the sliding glass (loose unrestrained glass industry system, water edge mill) of the wide 65mm of thick 1.3mm, long 165mm, make assess sample.Placed 30 minutes stacked back, uses universal tensile testing machine to peel off with the condition of 90 ° of peeling rate 300mm/ minutes, peel angle then, measures the bounding force of this moment.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
Above-mentioned result is as shown in table 3.
Table 3
Peel off static voltage [kV] Bounding force [N/25mm]
EXAMPLE III-1 0.1 2.9
EXAMPLE III-2 0.2 4.3
EXAMPLE III-3 0.2 8.5
EXAMPLE III-4 0.1 2.9
EXAMPLE III-5 0.2 4.3
EXAMPLE III-6 0.2 8.5
Comparative Example I II-1 1.2 2.2
Comparative Example I II-2 1.2 4.5
Comparative Example I II-3 1.2 7.8
By the result of above-mentioned table 3 as can be known, the adhesion type optics of embodiments of the invention III-1～6 is compared with Comparative Example I II-1～3, can suppress to peel off static voltage.In addition, the adhesion type optics of embodiments of the invention III-1～6 demonstrates and the equal bounding force in Comparative Example I II-1～3.Therefore, the adhesion type optics of EXAMPLE III-1～6 is the outstanding adhesion type opticses of static electricity resistance and low contaminative as can be known.
[EXAMPLE IV]
The modulation of＜acrylic polymers 〉
(acrylic polymers)
As the acrylic polymers (A) of EXAMPLE IV, use acrylic polymers (A) solution (40 weight %) of the acrylic polymers A (Tg=-68 ℃, weight-average molecular weight is 500,000, acid number is 0) of the Production Example I-1 in the example I.
(acrylic polymers (B))
In the four-hole boiling flask that is provided with stirring rake, thermometer, nitrogen ingress pipe, condenser, put into vinylformic acid ester in the different ninth of the ten Heavenly Stems 200 weight parts, vinylformic acid 2-hydroxyethyl ester 8 weight parts, as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate, 0.4 weight part and vinyl acetic monomer 312 weight parts, slowly stir and import nitrogen, liquid temperature in the flask is remained near 65 ℃, carried out polyreaction 6 hours, modulation acrylic polymers (B) solution (40 weight %).Tg=-80 ℃ of this acrylic polymers (B), weight-average molecular weight are 540,000, and acid number is 0.0.
The modulation of＜ionic liquid 〉
(ionic liquid (1))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add after the 5 weight % aqueous solution of four n-pentyl ammonium bromides (Tokyo changes into the industry system), 10 weight parts, in the rotation stirring rake, slowly add the 50 weight % aqueous solution of trifluoromethayl sulfonic acid lithium (Tokyo changes into the industry system) 5 weight parts.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours at 23 ℃.After removing its supernatant liquor, drying is 2 hours under 110 ℃ environment, obtains being liquid ionic liquid (1) 6.5 weight part down at 23 ℃.
To the ionic liquid (1) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying and confirming as is four n-pentyl ammonium trifluoro-methanyl sulfonates.In addition, estimate the toluene solubility, results verification goes out to have the toluene solubility.
(ionic liquid (2))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add four n-hexyl ammonium bromides (Tokyo changes into the industry system), 10 weight parts, then add distilled water 40 weight parts and methylene dichloride 50 weight parts, in the rotation stirring rake, slowly add the 50 weight % aqueous solution of trifluoromethayl sulfonic acid lithium (Tokyo changes into the industry system) 4 weight parts then.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours at 23 ℃.Then remove its supernatant liquor, obtain the methylene dichloride solute.
Clean the methylene dichloride solute that obtains 2 times with the distilled water of 100 weight parts, after methylene dichloride is removed in extraction, under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (2) 10 weight parts down at 23 ℃.
To the ionic liquid (2) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is four n-hexyl ammonium trifluoro-methanyl sulfonates.In addition, estimate the toluene solubility, results verification goes out to have the toluene solubility.
(ionic liquid (3))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add tetra n-heptyl ammonium bromide (Tokyo changes into the industry system) 10 weight parts, then add distilled water 70 weight parts and methylene dichloride 50 weight parts, in the rotation stirring rake, slowly add the 50 weight % aqueous solution of trifluoromethayl sulfonic acid lithium (Tokyo changes into the industry system) 4 weight parts then.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours at 23 ℃.Then remove its supernatant liquor, obtain the methylene dichloride solute.
Clean the methylene dichloride solute that obtains 2 times with the distilled water of 100 weight parts, after methylene dichloride is removed in extraction, under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (3) 11 weight parts down at 23 ℃.
To the ionic liquid (3) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is the tetra n-heptyl ammonium trifluoro-methanyl sulfonate.In addition, estimate the toluene solubility, results verification goes out to have the toluene solubility.
(ionic liquid (4))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add four Zheng Xin Ji Phosphonium bromides (Tokyo changes into the industry system), 10 weight parts, then add distilled water 200 weight parts and methylene dichloride 50 weight parts, in the rotation stirring rake, slowly add the 50 weight % aqueous solution of trifluoromethayl sulfonic acid lithium (Tokyo changes into the industry system) 3 weight parts then.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours at 23 ℃.Then remove its supernatant liquor, obtain the methylene dichloride solute.
Clean the methylene dichloride solute that obtains 2 times with the distilled water of 100 weight parts, after methylene dichloride is removed in extraction, under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (4) 10 weight parts down at 23 ℃.
To the ionic liquid (4) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is four Zheng Xin Ji Phosphonium trifluoro-methanyl sulfonates.In addition, estimate the toluene solubility, results verification goes out to have the toluene solubility.
(ionic liquid (5))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add the 5 weight % aqueous solution of four n-pentyl ammonium bromides (Tokyo changes into the industry system), 10 weight parts, in the rotation stirring rake, slowly add the 50 weight % aqueous solution of two (trifluoromethayl sulfonic acid) imines lithiums (キ シ ダ chemistry system) 9 weight parts then.After the interpolation, continue down to stir 1 hour, add methylene dichloride 70 weight parts then, further stirred 1 hour, left standstill then 12 hours at 23 ℃.Then remove its supernatant liquor, obtain the methylene dichloride solute.
Clean the methylene dichloride solute that obtains 3 times with the distilled water of 100 weight parts, after methylene dichloride is removed in extraction, under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (5) 15 weight parts down at 23 ℃.
To the ionic liquid (5) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is two (trifluoromethayl sulfonic acid) imines of four n-pentyl ammoniums.In addition, estimate the toluene solubility, results verification goes out not have the toluene solubility.
(ionic liquid (6))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, add the 20 weight % aqueous solution of 1-butyl-3-picoline muriate (pure pharmaceutical worker already makes with light) 10 weight parts, in the rotation stirring rake, slowly add the 20 weight % aqueous solution of two (trifluoromethayl sulfonic acid) imines lithiums (キ シ ダ chemistry system) 19 weight parts then.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours at 23 ℃.Then remove its supernatant liquor, obtain liquid product.
Clean the liquid product that obtains 3 times with the distilled water of 100 weight parts, then under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (6) 20 weight parts down at 23 ℃.
To the ionic liquid (6) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is two (trifluoromethayl sulfonic acid) imines of 1-butyl-3-picoline.In addition, estimate the toluene solubility, results verification goes out not have the toluene solubility.
The modulation of＜antistatic agent solution 〉
(antistatic agent solution (a))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser, put into lithium perchlorate 0.1 weight part, polypropylene glycol (diol type, number-average molecular weight: 2000) 9.9 weight parts, vinyl acetic monomer 10 weight parts, liquid temperature in the flask is remained near 80 ℃, mix and stirred 2 hours, modulation antistatic agent solution (a) (50 weight %).
＜anti-electrostatic is handled the making of film 〉
The anti-electrostatic of Production Example II-7 in the example II is handled film handle film as the anti-electrostatic in the EXAMPLE IV.
EXAMPLE IV-1
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add isocyanuric acid ester body (the Japanese polyurethane industry system of above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts, hexamethylene diisocyanate, Coronate HX) 0.6 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, under 25 ℃, mixed stir about 1 minute, modulation acryloid cement solution (1).
(making of adhesive sheet)
The above-mentioned anti-electrostatic of aforesaid propylene acid binder solution (1) coating is handled on the face opposite with the anti-electrostatic treated side of film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃.Then, the applying single face has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated on the surface of above-mentioned binder layer, is made into adhesive sheet.
EXAMPLE IV-2
(modulation of binder composition)
Except using above-mentioned ionic liquid (2) (10 weight % toluene solution) 6 weight parts to replace similarly modulating acryloid cement solution (2) with EXAMPLE IV-1 above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (2) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
EXAMPLE IV-3
(modulation of binder composition)
Except using above-mentioned ionic liquid (3) (10 weight % toluene solution) 6 weight parts to replace similarly modulating acryloid cement solution (3) with EXAMPLE IV-1 above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (3) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
EXAMPLE IV-4
(modulation of binder composition)
Except using above-mentioned ionic liquid (4) (10 weight % toluene solution) 16 weight parts to replace similarly modulating acryloid cement solution (4) with EXAMPLE IV-1 above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (4) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
EXAMPLE IV-5
(modulation of binder composition)
Use is diluted to 20 weight % with vinyl acetic monomer with aforesaid propylene acids polymkeric substance (B) solution (40 weight %) and solution 100 weight parts that obtain, and replace aforesaid propylene acids polymkeric substance (A) solution (40 weight %) being diluted to resulting solution 100 weight parts of 20 weight % with vinyl acetic monomer with this, in addition, similarly modulate acryloid cement solution (5) with EXAMPLE IV-1.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (5) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
Comparative Example I V-1
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add isocyanuric acid ester body (the Japanese polyurethane industry system of hexamethylene diisocyanate, Coronate HX) 0.8 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, under 25 ℃, mixed stir about 1 minute, modulation acryloid cement solution (6).
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (6) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
Comparative Example I V-2
(modulation of binder composition)
Use is diluted to 20 weight % with vinyl acetic monomer with aforesaid propylene acids polymkeric substance (B) solution (40 weight %) and solution 100 weight parts that obtain, and replace aforesaid propylene acids polymkeric substance (A) solution (40 weight %) being diluted to resulting solution 100 weight parts of 20 weight % with vinyl acetic monomer with this, in addition, similarly modulate acryloid cement solution (7) with Comparative Example I V-1.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (7) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
Comparative Example I V-3
(modulation of binder composition)
Except using above-mentioned ionic liquid (5) (10 weight % toluene solution) 2 weight parts to replace similarly modulating acryloid cement solution (8) with EXAMPLE IV-1 above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (8) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
Comparative Example I V-4
(modulation of binder composition)
Except using above-mentioned ionic liquid (6) (10 weight % toluene solution) 2 weight parts to replace similarly modulating acryloid cement solution (9) with EXAMPLE IV-1 above-mentioned ionic liquid (1) (10 weight % toluene solution) 2 weight parts.
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (9) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
Comparative Example I V-5
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add isocyanuric acid ester body (the Japanese polyurethane industry system of above-mentioned antistatic agent solution (a) (50 weight %) 2.6 weight parts, hexamethylene diisocyanate, Coronate HX) 0.4 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, under 25 ℃, mixed stir about 1 minute, modulation acryloid cement solution (10).
(making of adhesive sheet)
Except using aforesaid propylene acid binder solution (10) replacement aforesaid propylene acid binder solution (1), and EXAMPLE IV-1 is similarly made adhesive sheet.
About the adhesive sheet that in the above embodiments, comparative example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.
＜peel off the measurement of static voltage 〉
Adhesive sheet is cut into the size of wide 70mm, long 130mm, after peeling off barrier sheet, so that exposing the mode of 30mm, the end of one side is crimped on polaroid (day eastern electrician's system with pulling cylinder, SEG1224DUARC150T, wide: 70mm, length: 100mm) on the surface, wherein, described polaroid has been fitted in that to have eliminated the electrostatic acrylic panel in advance (thick: 1mm, wide: 70mm, length: 100mm).
After under the environment of 23 ℃ * 50%RH, placing 1 day, as shown in Figure 1, sample is arranged on the prescribed position.The end that to expose the side of 30mm is fixed on the sutomatic winding machine, peels off with the condition of 150 ° of peel angle, peeling rate 10m/min.Use is fixed on electric potential measuring instrument on the prescribed position, and (springtime motor system KSD-0103) is measured the current potential on the polaroid surface that produces this moment.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
The evaluation of＜contaminative 〉
Adhesive sheet is cut into the size of wide 70mm, long 100mm, under the state that has bubble to sneak between above-mentioned adhesive sheet and the polaroid, be fitted in the use fluorine cpd with hand and implemented surface-treated polaroid (day eastern electrician's system, SEG1424DURACT150T, wide: 70mm, length: as 100mm) on the surface, to make assess sample.
Under the environment of 50 ℃ * 92%RH, placed this assess sample 24 hours, and then under the environment of 23 ℃ * 50%RH, placed 2 hours, subsequently with hand release adhesive sheet from the adherend, the visual pollutional condition of observing adherend surface at this moment down.Metewand is as follows.
In the time of can not confirming to pollute: zero
When confirming to pollute: *
＜bonding force measurement 〉
(Fujiphoto system, thick: 90 μ m) be cut into wide 70mm, long 100mm, dipping is 1 minute in 60 ℃ aqueous sodium hydroxide solutions (10 weight %), cleans with distilled water, makes adherend with the cellulose triacetate film.
Placed above-mentioned adherend 24 hours under the environment of 23 ℃ * 50%RH, the adhesive sheet that uses the pressure of 0.25MPa will be cut into wide 25mm, long 100mm then is layered on the above-mentioned adherend making assess sample.
Carry out above-mentioned stacked after, under the environment of 23 ℃ * 50%RH, placed 30 minutes, use universal tensile testing machine to peel off then with the condition of 180 ° of peeling rate 10m/ minutes, peel angle, measure the bounding force of this moment.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
About the adhesive sheet that in the above embodiments, comparative example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.Its result is as shown in table 4.
Table 4
Peel off static voltage [kV] Contaminative [-] Bounding force [N/25mm]
EXAMPLE IV-1 -0.2 ○ 0.8
EXAMPLE IV-2 -0.2 ○ 0.7
EXAMPLE IV-3 -0.4 ○ 0.7
EXAMPLE IV-4 -0.2 ○ 0.7
EXAMPLE IV-5 -0.2 ○ 0.8
Comparative Example I V-1 -0.9 ○ 0.6
Comparative Example I V-2 -1.0 ○ 0.7
Comparative Example I V-3 -1.1 ○ 1.3
Comparative Example I V-4 -1.3 × 0.6
Comparative Example I V-5 -0.5 × 0.3
By the result of above-mentioned table 4 as can be known, when using the binder composition of making according to the present invention (EXAMPLE IV-1～5), in all embodiment, the static voltage of peeling off of polaroid has been obtained inhibition, and occurred polluting.
Be directed to this, when not using ionic liquid (Comparative Example I V-1～2), although all occur to pollute, to implemented with fluoro-resin the surface-treated polaroid to peel off static voltage higher.In addition, when using the ionic liquid do not have the toluene solubility (Comparative Example I V-3～4), occurred peeling off the higher result of static voltage to what implement the surface-treated polaroid with fluoro-resin.In addition, when using the antistatic agent (Comparative Example I V-5) that constitutes by polyether polyol and an alkali metal salt, obtained inhibition, the result of pollution occurred taking place although peel off static voltage.Therefore, in comparative example, all can't accomplish simultaneously to suppress to as the polaroid of adherend peel off static voltage the time suppress to pollute, be not suitable for use in the adhesive sheet binder composition.
In addition, the adhesive sheet of embodiments of the invention IV-1～5, its 180 ° of peel adhesion in the scope of 0.1～6N/25mm, are can be as the adhesive sheet of adhesive sheet all.
[EXAMPLE V]
The modulation of＜acrylic polymers 〉
(acrylic polymers (A))
As the acrylic polymers (A) of EXAMPLE V, use acrylic polymers (A) solution (40 weight %) of the acrylic polymers A (Tg=-68 ℃, weight-average molecular weight is 500,000, acid number is 0) of the Production Example I-1 in the example I.
The modulation of＜ionic liquid 〉
(ionic liquid (1))
In the four-hole boiling flask that is provided with stirring rake, thermometer, condenser; interpolation is diluted to the solution of 20 weight % with distilled water with 1-butyl-3-picoline muriate (pure pharmaceutical worker already makes with light) 10 weight parts; in the rotation stirring rake, add slowly that with distilled water two (trifluoromethane sulfonyl group) imines lithiums (キ シ ダ chemistry system) 19 weight parts are diluted to the solution of 20 weight % then.After the interpolation, continue down to stir 2 hours, left standstill then 12 hours, remove its supernatant liquor, obtain liquid product at 25 ℃.
Clean the liquid product that obtains 3 times with the distilled water of 100 weight parts, then under 110 ℃ environment dry 2 hours, obtain being liquid ionic liquid (1) 20 weight part down at 25 ℃.To the ionic liquid (1) that obtains carry out NMR ( 1H, 13C) measurement, FT-IR measure, XRF measures, and identifying, confirming as is two (trifluoromethane sulfonyl group) imines of 1-butyl-3-picoline.
(antistatic agent solution (e))
The mixed solvent that use is made of vinyl acetic monomer 20 weight parts and Virahol 20 weight parts, (Tokyo changes into the industry system as the lauryl trimethyl ammonium muriate of cationic tensio-active agent in dilution, 25 ℃ down for solid-state) 10 weight parts, modulate antistatic agent solution (e) (20 weight %) thus.
(antistatic agent solution (f))
As the antistatic agent solution (f) of Production Example V, use the antistatic agent solution (50 weight %) of the antistatic agent A of the Production Example I-5 in the example I.
＜anti-electrostatic is handled the making of film 〉
The anti-electrostatic of Production Example II-7 in the example II is handled film handle film as the anti-electrostatic in the EXAMPLE IV.
EXAMPLE V-1
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add alicyclic ionic liquid solution (wide flourish chemical industry system, the 10 weight % vinyl acetic monomer solution of IL-C1) 0.6 weight part, isocyanuric acid ester body (Japanese polyurethane industry system as the hexamethylene diisocyanate of linking agent, Coronate HX) 0.6 weight part, dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part as crosslinking catalyst, mixed stir about 1 minute down at 25 ℃, modulation acryloid cement solution (1).
(making of adhesive sheet)
Aforesaid propylene acid binder solution (1) is coated in above-mentioned anti-electrostatic handles on the face opposite of film, heated 3 minutes down, form the binder layer of thick 20 μ m at 110 ℃ with the anti-electrostatic treated side.Then, the applying single face has been implemented the silicone-treated face of pet film of the thick 25 μ m of silicone-treated on the surface of above-mentioned binder layer, makes adhesive sheet.
EXAMPLE V-2
(modulation of binder composition)
Use alicyclic ionic liquid (wide flourish chemical industry system, the 10 weight % vinyl acetic monomer solution of IL-C3) 0.6 weight part replaces above-mentioned alicyclic ionic liquid (wide flourish chemical industry system, the 10 weight % vinyl acetic monomer solution of IL-C1) 0.6 weight part, in addition, similarly modulate acryloid cement solution (2) with EXAMPLE V-1.
(making of adhesive sheet)
Except using above-mentioned acryloid cement solution (2) replacement aforesaid propylene acid binder solution (1), and EXAMPLE V-1 is similarly made adhesive sheet.
Comparative example V-1
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add isocyanuric acid ester body (Japanese polyurethane industry system as the hexamethylene diisocyanate of linking agent, Coronate HX) 0.6 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, mixed stir about 1 minute down at 25 ℃, modulation acryloid cement solution (6).
(making of adhesive sheet)
Except using above-mentioned acryloid cement solution (6) replacement aforesaid propylene acid binder solution (1), and EXAMPLE V-1 is similarly made adhesive sheet.
Comparative example V-2
(modulation of binder composition)
Use 10 weight % vinyl acetic monomer solution, 0.6 weight part of above-mentioned ionic liquid (1) to replace above-mentioned alicyclic ionic liquid (the 10 weight % vinyl acetic monomer solution of IL-C1) 0.6 weight part, in addition, similarly modulate acryloid cement solution (7) with EXAMPLE V-1.
(making of adhesive sheet)
Except using above-mentioned acryloid cement solution (7) replacement aforesaid propylene acid binder solution (1), and EXAMPLE V-1 is similarly made adhesive sheet.
Comparative example V-5
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add above-mentioned antistatic agent solution (e) (20 weight %) 0.3 weight part, as isocyanuric acid ester body (the Japanese polyurethane industry system of the hexamethylene diisocyanate of linking agent, Coronate HX) 0.5 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, mixed stir about 1 minute down at 25 ℃, modulation acryloid cement solution (10).
(making of adhesive sheet)
Except using above-mentioned acryloid cement solution (10) replacement aforesaid propylene acid binder solution (1), and EXAMPLE V-1 is similarly made adhesive sheet.
Comparative example V-6
(modulation of binder composition)
With vinyl acetic monomer aforesaid propylene acids polymkeric substance (A) solution (40 weight %) is diluted to 20 weight %, in these solution 100 weight parts, add above-mentioned antistatic agent solution (f) (50 weight %) 4 weight parts, as TriMethylolPropane(TMP)/toluene support vulcabond 3 aggressiveness affixtures (Japanese polyurethane industry system of linking agent, trade(brand)name Coronate L) 0.53 weight part, as dibutyl tin laurate (the vinyl acetic monomer solution of 1 weight %) 0.4 weight part of crosslinking catalyst, mixed stir about 1 minute down at 25 ℃, modulation acryloid cement solution (11).
(making of adhesive sheet)
Except using above-mentioned acryloid cement solution (11) replacement aforesaid propylene acid binder solution (1), and EXAMPLE V-1 is similarly made adhesive sheet.
About the adhesive sheet that in the above embodiments, comparative example, obtains, peel off static voltage, contaminative and bounding force by following main points evaluation.
＜peel off the measurement of static voltage 〉
Adhesive sheet is cut into the size of wide 70mm, long 130mm, after peeling off barrier sheet, so that exposing the mode of 30mm, the end of one side is crimped on polaroid (day eastern electrician's system with pulling cylinder, SEG1425EWVAGS2B (non-glare treated type) or SEG1425EWV (without the non-glare treated type), wide: 70mm, length: 100mm) on the surface, wherein, described polaroid has been fitted in and has eliminated electrostatic acrylic panel (the レ イ ヨ of Mitsubishi Application system in advance, ア Network リ ラ イ ト is thick: 1mm, wide: 70mm, length: 100mm).
After under the environment of 23 ℃ * 50%RH, placing 1 day, as shown in Figure 1, sample is arranged on the prescribed position.The end that to expose the side of 30mm is fixed on the sutomatic winding machine, peels off with the condition of 150 ° of peel angle, peeling rate 10m/min.Use is fixed on electric potential measuring instrument on the prescribed position, and (springtime motor system KSD-0103) is measured the current potential on the polaroid surface that produces this moment.Measurement is to carry out under the environment of 23 ℃ * 50%RH.
The evaluation of＜contaminative 〉
Adhesive sheet is cut into the size of wide 100mm, long 100mm, use pulls cylinder and is crimped on and fits in acrylic panel (day eastern resin industry system, CLAREX (deceiving), thick: 1mm, wide: 180mm, length: (day eastern electrician's system of the polaroid 250mm), SEG1425EWVAGS2B, wide: 180mm, length: as 250mm) on the surface, to make assess sample.
Under the environment of 23 ℃ * 50%RH, placed this assess sample 1 month, subsequently with hand release adhesive sheet from the adherend, the visual pollutional condition of observing the adherend surface of this moment down.Metewand is as follows.
In the time of can not confirming to pollute: zero
When confirming to pollute: *
＜bonding force measurement 〉
The measuring method of the bounding force in the EXAMPLE V is identical with the above embodiments IV.
Above-mentioned result is as shown in table 5.
Table 5
Figure BDA0000077455830000751
By the result of above-mentioned table 5 as can be known, when using the binder composition of making according to the present invention (EXAMPLE V-1～2), in all embodiment, the static voltage of peeling off of polaroid has all been obtained inhibition, and on polaroid, do not occur polluting, and then have outstanding releasable.
Be directed to this, when not using ionic liquid (comparative example V-1),, occurred polaroid peeled off the higher result of static voltage although occur to pollute.In addition, when use does not have alicyclic ionic liquid (comparative example V-2), occurred making following two kinds to suppress the results of variation simultaneously, promptly to the inhibition of peeling off static voltage and the inhibition of two types polaroid to polluting.In addition, when with tensio-active agent (comparative example V-5) when the antistatic agent, and when using the antistatic agent that constitutes by polyether polyol and an alkali metal salt (comparative example V-6), although can suppress to peel off static voltage, pollution has taken place.Therefore, in comparative example, all can't suppress simultaneously to as the polaroid of two kinds of double-types of adherend peel off static voltage and pollution, be not suitable for the binder composition that adhesive sheet is used.

Claims (16)

1. a binder composition is characterized in that, contain ionic liquid and be polymkeric substance below 0 ℃ as the second-order transition temperature Tg of base polymer,
Described second-order transition temperature Tg obtains by following formula,
Formula: 1/ (Tg+273)=∑ [Wn/ (Tgn+273)]
In the formula, Tg represents the second-order transition temperature of multipolymer, and Wn represents each monomeric weight fraction, and Tgn represents the second-order transition temperature of the homopolymer that formed by each monomer, and n represents each monomeric kind.
2. binder composition according to claim 1 is characterized in that, described ionic liquid is to contain nitrogen salt, contain more than in sulfosalt or the phosphorous salts any one.
3. binder composition according to claim 2 is characterized in that, contains more than one positively charged ion of useful following general formula (A)～(D) expression in the described ionic liquid,
R in the formula (A) aThe expression carbonatoms is 4～20 alkyl, can contain heteroatoms, R bAnd R cIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms, wherein, when nitrogen-atoms contains two key, do not have R c
R in the formula (B) dThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R e, R fAnd R gIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms;
R in the formula (C) hThe expression carbonatoms is 2～20 alkyl, can contain heteroatoms, R i, R jAnd R kIdentical or different, expression hydrogen or carbonatoms are 1～16 alkyl, can contain heteroatoms;
Z in the formula (D) represents nitrogen, sulphur or phosphorus atom, R l, R m, R nAnd R oIdentical or different, the expression carbonatoms is 1～20 alkyl, can contain heteroatoms, wherein, when Z is sulphur atom, does not have R o
4. binder composition according to claim 1 is characterized in that, described ionic liquid is a toluene soluble ion liquid.
5. binder composition according to claim 4 is characterized in that described ionic liquid contains CF 3SO 3 -Negatively charged ion.
6. binder composition according to claim 1 is characterized in that, described ionic liquid is alicyclic ionic liquid.
7. binder composition according to claim 6 is characterized in that, described ionic liquid contains any in tetramethyleneimine positively charged ion and/or the piperidines positively charged ion.
8. binder composition according to claim 1, it is characterized in that, described second-order transition temperature is the polymkeric substance below 0 ℃, be with have in acrylate that carbonatoms is 1～14 alkyl and/or the methacrylic ester more than a kind as (methyl) acrylic polymers of principal constituent.
9. binder composition according to claim 8 is characterized in that, the acid number of described (methyl) acrylic polymers is below 1.0.
10. a binder layer is characterized in that, contains any described binder composition in the claim 1～9.
11. an adhesive sheets is characterized in that, has the binder layer that comprises any described binder composition in the claim 1～9 on the single or double of supporter.
12. adhesive sheets according to claim 11 is characterized in that, described supporter possesses implements the plastics film that anti-electrostatic is handled.
13. a surface protective film is characterized in that, has the binder layer that comprises any described binder composition in the claim 1～9 on the single or double of supporter.
14. surface protective film according to claim 13 is characterized in that, described supporter possesses implements the plastics film that anti-electrostatic is handled.
15. an adhesion type optics is characterized in that, has the binder layer that comprises any described binder composition in the claim 1～9 on the single or double of optics.
16. adhesion type optics according to claim 15 is characterized in that, described optics comprises polaroid, polarizer, brightness improving plate or antiglare sheet.
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